JP5613763B2 - Solvents, solutions, cleaning compositions and methods - Google Patents

Description

  This application claims the benefit of US Provisional Patent Application No. 61 / 182,407, filed May 29, 2009.

  The present invention relates to formulated compositions useful as cleaning products or for other applications, which include certain alkyl ketal ester compounds.

  A number of formulated products are produced and sold. One broad category of these products includes various types of cleaning products, which can be used for industrial, household or other cleaning applications.

  The prior art of cleaning agents is rich in variety. Numerous detergent and detergent references discuss various formulations that can be made as an aqueous solution, aqueous concentrate, powder or solid formulation of the cleaning composition. The various uses of such cleaners that have been made to date include hard surface cleaners, manual and automatic dishwasher formulations, laundry formulations, pan and pan oil cleaner formulations, floors Cleaning agents, glass cleaners, skin cleaners, shampoos and the like. Such formulations tend to contain various ingredients, but often contain at least a surfactant and may contain one or more accelerator additives or solvent components. The cleaning agent can optionally include builders, sequestering agents, second solvents, bleaching agents (chlorine or oxygen based), and other non-functional ingredients such as perfumes, dyes.

  Because these various types of products are very different as well as the conditions under which they are used, individual products tend to be formulated specifically for the intended end use application. In each case, there are several concerns that drive formulation selection.

  Of course, the effectiveness of a product that can be defined as the product can perform its intended function (s) is of course a fundamental concern.

  In some cases, additional constraints are desired by preventing certain types of substances from being included in the product. For example, many products are re-formulated to remove volatile organic chemicals, including at least some common organic solvents. In some products it is necessary to eliminate or minimize water. In still other products, there may be a need to exclude other specific substances for various reasons.

  In other cases, it is desirable to replace chemicals based on fossil fuels with chemicals derived from raw materials that are renewable every year.

Of course, price is always a concern.

  In many cases, the physical form of the product is also important. The physical form of a product can be constrained by the usage of the product. Certain applications may require products in the form of low viscosity liquids, high viscosity liquids, creams, pastes, gels, powders, and even solids.

  These formulated products often contain components that are immiscible with each other or have very limited miscibility. This is generally seen in aqueous systems that also contain oils or other highly non-polar components. This immiscibility can cause at least two problems. The first is to formulate immiscible substances to produce the required product form for a particular application, especially when the required product form is a low viscosity liquid or a clear liquid or gel. It can be difficult. The second problem is that even if the correct product form can be obtained, the components may gradually separate into multiple layers. Layer separation is a very important issue because products are usually stored for weeks or months until they reach the consumer and may not be used immediately thereafter. To avoid these problems, it is often necessary to introduce various types of emulsifiers, dispersants, thickeners or cosolvents into these products. This introduces complexity, increases costs, and in some cases may detract from other objectives such as reducing or eliminating volatile organic chemicals.

  Applicants have discovered that certain alkyl ketal esters contained in Structure I below are excellent formulation ingredients that provide benefits for many formulated products. This alkyl ketal ester is an excellent solvent for a wide range of materials. Many of them are miscible with water or other organic solvents, or both. The alkyl ketal esters described herein have low volatility. Under normal conditions of manufacture, storage, and use, the alkyl ketal ester typically does not react with many other materials commonly found in formulated products.

  Because of these properties, alkyl ketal esters can be used in a wide range of detergent compositions or formulations. In some cases, the alkyl ketal ester itself can function as a cleaning agent due to its solubility in various types of soils and fats and oils, and can provide improved cleaning properties to the cleaning product. In other cases, the alkyl ketal ester according to structure I can function primarily as a solvent, co-solvent or emulsifier for one or more other components in the product formulation. The alkyl ketal ester can optionally function to solubilize one or more ingredients in the product formulation or in a solvent or carrier liquid. In other cases, the alkyl ketal ester can compatibilize one or more components with other components of the product formulation, for example, to form an emulsion that can be very storage stable. The alkyl ketal ester (s) may in some cases reduce or eliminate unwanted components such as volatile organic compounds while allowing incompatible materials to be formulated into a stable form.

  This alkyl ketal ester has the following properties in cleaning product formulations: stability in many aqueous solutions or in some aqueous solutions; stability in many non-aqueous solutions; compatibility with chlorine-based or oxygen-based bleaches One or more of the properties; compatibility with many formulation ingredients commonly found in pharmaceutical products; and the effectiveness of removing various soils from many substrates.

  In one aspect, the present invention provides a solute solution in an aqueous co-solvent mixture comprising water and at least one alkyl ketal ester according to structure I below that is miscible in their relative proportions to the water present in the solution. Is described.

  “Solution” means a “true” solution, where the components are homogeneously mixed at the molecular level, or any other macroscopically homogeneous mixture, where the solute is above the visible light wavelength. Exist in the form of small droplets and the mixture is transparent. If the molecules are not dispersed, the solute must be present in the form of droplets smaller than about 200 nm.

  The term “miscible” and variations thereof (such as “miscibility”) are used herein as synonyms for “solubility” as the term is defined above. A substance may be completely or partially miscible with another substance. As used herein, a substance that is said to be miscible with another substance does not require additional qualities and is miscible with other substances in all proportions. That is, a mixture containing only two components forms a clear, uniform solution at a total weight ratio of 99.9: 0.1 to 0.1: 99.9. A substance is said to be highly miscible with another substance when solubilized in this other substance to the extent of at least 20% relative to 80% of the other substance, and at least It is preferred that other materials are soluble to the extent of 50%. A “highly miscible” material may be soluble in other materials to a total proportion of up to 99.9% relative to 0.1% of other materials and lower. A substance is incompatible with another substance if it is immiscible with it (as defined below) or otherwise does not dissolve in another substance to the extent of 20% with respect to 80% of the other substance. It is said to be “slightly miscible” (or have “low miscibility”). Substances with slightly low miscibility may be dissolved in other substances to the extent of only 10% with respect to 90% of other substances and to other substances to a degree of only 5% with respect to 95% of other substances. It may be dissolved. A substance is said to be “immiscible” with another substance if it does not itself dissolve in another substance to the extent of at least 1% relative to 99% of the other substance. Unless otherwise stated, miscibility is assessed at 25 ° C.

  “Macroscopically uniform” means that the composition is uniform when viewed on a length scale of at least 10 μm.

  Very often, the co-solvent mixture contains water and the alkyl ketal ester, and the solute is the least miscible with water. In such cases, the co-solvent mixture of the present invention is often a better solvent for the solute than water itself. This superior solvent effect can dissolve more solutes than can only be dissolved in water, thus forming a higher concentration solute solution than can be formed in water alone. be able to. In some cases, the improved solubility extends the temperature range in which the solute (s) can remain dissolved. In some embodiments, the presence of the alkyl ketal ester can improve low temperature stability or high temperature stability. This property can extend the tolerance of the temperature range in which the solution can be stored and used. The ability to maintain a stable solution over a wide temperature range is particularly important in cleaning products that contain nonionic surfactants. Nonionic surfactants tend to be less water soluble as the temperature increases, and therefore conventional products containing those surfactants are either turbid or separated into layers when the solution is heated. Often causes the problem of forming more. In other cases, surfactants become less water soluble as the temperature decreases, and products containing these surfactants often become cloudy or form separate layers as the solution cools. . The presence of an alkyl ketal ester often reduces the tendency of the aqueous solution containing the surfactant to become cloudy or separate during cooling.

  Solutions according to this aspect of the invention may constitute all or part of any of the general types of formulated cleaning products described herein, or all or part of another type of product. It may be configured.

  Additional materials that are highly water miscible may be present in the solution of this aspect of the invention, as described in more detail below. For example, both water and ethanol can be present with at least one alkyl ketal ester and at least one solute.

  Two or more alkyl ketal esters according to structure I below can be present in the solution of this aspect of the invention. In certain embodiments, there is at least one highly water miscible alkyl ketal ester and at least one slightly less water miscible alkyl ketal ester.

  An aqueous co-solvent mixture comprising water and the alkyl ketal ester is also useful as a continuous or co-continuous phase in the emulsion. The term “emulsion” is used herein to denote a mixture of two or more immiscible liquid phases, wherein (a) one of these phases is continuous, and At least one is dispersed in the continuous phase or (b) these phases are co-continuous. This dispersed phase should be dispersed in droplets of about 1 mm and preferably have a diameter on the order of 100 μm. Emulsions are generally macroscopically uniform in the composition. Thus, in another aspect, the invention is an emulsion comprising at least one continuous phase and at least one dispersion phase, or a first co-continuous phase and a second co-continuous phase, wherein at least 1 One continuous or co-continuous phase comprises a co-solvent mixture comprising water and an alkyl ketal ester according to structure I below.

  Thus, in another aspect, the invention is an emulsion comprising at least one continuous phase comprising water and an alkyl ketal ester, wherein the alkyl ketal ester is in their relative proportion present in the continuous phase. It is miscible with water.

  In another aspect, the invention is a composition comprising a surfactant and an alkyl ketal ester according to structure I below. The composition can take any of several forms. For example, the surfactant can be dissolved in the alkyl ketal ester and vice versa. The surfactant and alkyl ketal ester may form a single phase mixture (ie, a solution) with one or more additional components, in which water is an important example. The alkyl ketal ester may form a continuous phase or be present in the continuous phase (ie, remain in it) in which the surfactant is a micelle or other type of dispersed phase. Distributed in the form of The continuous phase in such cases consists entirely of the alkyl ketal ester, or the alkyl ketal ester may form a component of a cosolvent mixture that forms all or part of the continuous phase. In another form, the alkyl ketal ester and the surfactant, optionally together with other components, form the dispersed or co-continuous phase of the emulsion. The alkyl ketal ester and the surfactant can form separate co-continuous phases in the emulsion or can be present in those co-continuous phases. The surfactant can be present at least partially at the interface of the phase comprising the alkyl ketal ester and another phase. The surfactant / alkyl ketal ester composition may take the form of a solid, which may be in the form of particulates.

  These compositions may, of course, contain a wide number of components in addition to the surfactant and the alkyl ketal ester, as necessary or desired for the purpose for which the particular composition is intended. Depending on the nature of those additional ingredients, these compositions are useful in forming a wide range of pharmaceutical products, including a wide range of cleaning products, as described in more detail below.

  In another aspect, the present invention provides 20-99% by weight of water, 0.1-25% by weight of at least one alkyl ketal ester, and 0.1-20% by weight of at least one surfactant. %. It should be noted that throughout this specification, unless stated otherwise, all percentages are by weight and represent weight percent of the total composition. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

  In another aspect, the present invention is a cleaning formulation comprising 1-80% water, 1-40% alkyl ketal ester, and 0.1-10% surfactant. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

  In another aspect, the present invention provides (a) 40-75% by weight of water, (b) 0.1-25% by weight of at least one alkyl ketal ester, (c) at least one surfactant and A cleaning composition comprising at least one of components h), i), and o), wherein h), i), and o) are h) is at least one builder or chelating agent I) is at least one chlorine bleach or non-chlorine bleach, and o) is one or more abrasives. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types. In some embodiments, the cleaning composition of this aspect comprises up to 30% builder or chelating agent, up to 10% bleach, and up to 30% abrasive.

  In another embodiment, the present invention provides: a) 50-95% by weight of water, 0.1-25% by weight of at least one alkyl ketal ester, and 0.1-45% by weight of at least one surfactant. And a laundry liquid formulation comprising at least one of h), i), o), q) and r), wherein h), i), o), q) and r) are H) is at least one builder or chelating agent, i) is at least one chlorine bleach or non-chlorine bleach, o) is one or more abrasives, and q) is One or more anti-deposition agents and r) is one or more brighteners. The alkyl ketal ester suitably corresponds to the following formula I and may be a highly water miscible type, a slightly less water miscible type, or a mixture of both types. In some embodiments, the cleaning composition of this aspect comprises up to 30% builder or chelating agent, up to 10% bleach, and up to 30% abrasive.

  In another aspect, the present invention provides at least one surfactant, alkyl ketal ester, solid phase (including at least one of a carrier, abrasive, or solid bleach), and only 5% by weight of water A laundry powder detergent, a powder or granular dishwashing product, or a powder bleach detergent. The surfactant, alkyl ketal ester and water, if present, are supported on the solid phase. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

In a further aspect, the present invention is a personal care cleaning product comprising at least 20% by weight water, an alkyl ketal ester having the following structure I, and one or more components selected from s) -w), wherein And s) to w):
s) paraffin oil, naphthenic oil or aromatic mineral oil;
t) (melting point less than 45 ° C., molecular weight at least 190, at least one amide or ester group, and at least one alkyl chain (containing at least 8 carbon atoms), and water 99 Nonionic organic compounds having a water solubility of about 1% with respect to%;
u) Nonionic organic silicone compounds having a melting point of less than 45 ° C. and water solubility of about 1% with respect to 99% of water;
v) long chain alcohols;
w) Waxes.

  In another aspect, the invention is a cleaning composition comprising a substantial portion of an aqueous base, a substantially effective amount of a surfactant that removes soil, an effective amount of a sequestering agent that removes hardness, and an alkyl ketal ester. . The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

  In another aspect, the present invention is a dishwasher powder composition comprising an alkali source, an alkali stable surfactant, an alkali stable sequestering agent and an alkyl ketal ester. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

  In another aspect, the present invention is an aqueous dishwashing detergent for hand washing that is predominantly comprised of an aqueous medium, a surfactant, a hard sequestering agent, an alkali source, an alkyl ketal ester and a dye or fragrance. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

  In another aspect, the present invention is an aqueous gel formulation for a dishwasher comprising an alkali source, an alkyl ketal ester and an alkali stable aqueous thickener. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

  In another aspect, the invention is an aqueous hard surface cleaner comprising an aqueous base, an anionic and / or nonionic surfactant and an alkyl ketal ester. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

  In another aspect, the invention is an aqueous bactericidal detergent for hard surfaces comprising an aqueous base and an organic surfactant, an organic sequestering agent, an antimicrobial agent and an alkyl ketal ester. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

  In another aspect, the present invention is a pine oil-containing aqueous detergent that is predominantly water, pine oil, surfactants, bactericides, and alkyl ketal esters. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

  In another aspect, the present invention is a powder cleaner comprised predominantly of abrasive inorganic materials, surfactants, alkyl ketal esters, and chlorine or oxygen bleaches. This alkyl ketal ester suitably corresponds to structure I below.

  In another aspect, the present invention is an aqueous glass detergent composition comprised predominantly of water, lower alkanols and alkyl ketal esters. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

  In another aspect, the present invention is a spray-structure oven cleaner that is predominantly comprised of an aqueous base, a solvent mixture comprising an alkaline glycol ether solvent, an alkyl ketal ester, a sodium hydroxide source, and an alkali-stable surfactant. is there. The alkyl ketal ester suitably corresponds to structure I below and may be of a high water miscibility type, a slightly low water miscibility type, or a mixture of both types.

  In another aspect, the present invention is a method for cleaning a soil substrate, wherein the composition of any of the previous embodiments of the present invention is contacted with a soil substrate and then the cleaning agent is removed along with the removed soil. Removing the composition.

  In yet another aspect, the present invention is a method for increasing the turbidity point of a nonionic surfactant solution in water, to which a highly water-miscible alkyl ketal ester of structure I is added: It is a method including.

  The alkyl ketal ester has the formula I:

（式中、ａは０または１〜１２の整数であり；
ｂは０または１であり；
Ｒ^１は水素、１個以上のヘテロ原子で置換されていてもよい、１〜１８個の炭素原子を有する飽和または不飽和炭化水素基であり；
Ｒ^２、Ｒ^３、およびＲ^４は、独立して、メチレン、アルキルメチレン（このアルキル基は１個以上のヘテロ原子で置換されていてもよい）、またはジアルキルメチレン（これらのアルキル基のいずれかまたは両方は１個以上のヘテロ原子で置換されていてもよい）であり、
Ｒ^５は低級アルキルである）
を有する。

Wherein a is 0 or an integer from 1 to 12;
b is 0 or 1;
R ¹ is hydrogen, a saturated or unsaturated hydrocarbon group having from 1 to 18 carbon atoms, optionally substituted with one or more heteroatoms;
R ² , R ³ , and R ⁴ are independently methylene, alkylmethylene (the alkyl group may be substituted with one or more heteroatoms), or dialkylmethylene (any one of these alkyl groups). Or both may be substituted with one or more heteroatoms),
R ⁵ is lower alkyl)
Have

  When b is 0, the alkyl ketal ester contains a 5-membered ring, and when b is 1, it contains a 6-membered ring.

R ¹ may be hydrogen or a linear, branched and / or cyclic hydrocarbon group. The hydrocarbon group may be saturated or unsaturated. When unsaturated, the hydrocarbon group may contain an alkenyl group or an alkynyl group, or both, or may contain one or more aromatic rings or consist of one or more aromatic rings. R ¹ may be substituted with one or more heteroatoms. In some embodiments, R ¹ is preferably hydrogen or lower (C _1-4 ) alkyl, more preferably hydrogen or methyl.

R ² (if present) and R ⁴ are independently preferably methylene, ethylidene (> CH—CH ₃ ), or 2-hydroxyethylidene (> CH—CH ₂ OH). R ³ is preferably methylene, ethylidene, propylidene (> CH—CH ₂ —CH ₃ ),> CH—CH ₂ OH,> C (CH ₃ ) CH ₂ OH,> C (C ₂ H ₅ ) CH _{2. OH, is> C (CH 2 OH) 2} ,> CH-CH (OH) -CH 2 OH _{or> CH- (CHOH) 3 -CH 2} OH. In some embodiments, b is 0, R ⁴ is methylene, R ³ is methylene, 2-hydroxyethylidenemethylene,> C (CH ₃ ) CH ₂ OH or> C (C ₂ H ₅ ) CH. _{2 One of} OH.

R ⁵ preferably contains up to 4 carbon atoms, more preferably 1 or 2 carbon atoms.

  Preferred alkyl ketal esters include the reaction product of 1,2-ethylene glycol and methyl ester, ethyl ester, n-propyl ester or n-butyl ester of levulinic acid; methyl ester of 1,2-propylene glycol and levulinic acid Reaction product of ethyl ester, n-propyl ester or n-butyl ester; reaction product of 1,3-propanediol with methyl ester, ethyl ester, n-propyl ester or n-butyl ester of levulinic acid; Reaction product of glycerin with methyl ester, ethyl ester, n-propyl ester or n-butyl ester of levulinic acid; trimethylolethane with methyl ester, ethyl ester, n-propyl ester or n-butyl ester of levulinic acid Anti Product; reaction product of trimethylolpropane and methyl ester, ethyl ester, n-propyl ester or n-butyl ester of levulinic acid; methyl ester, ethyl ester, n-propyl ester or n- of pentaerythritol and levulinic acid Reaction product of butyl ester; reaction product of erythritol and levulinic acid methyl ester, ethyl ester, n-propyl ester or n-butyl ester; sorbitol and levulinic acid methyl ester, ethyl ester, n-propyl ester or Reaction product of n-butyl ester; reaction product of 1,2-ethylene glycol and methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate or n-butyl acetoacetate; 1,2-pro Reaction products of lenglycol with methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate or n-butyl acetoacetate; 1,3-propanediol and methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate or n Reaction product of butyl acetoacetate; reaction product of glycerin and methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate or n-butyl acetoacetate; trimethylolethane and methyl acetoacetate, ethyl acetoacetate, n -Reaction product of propyl acetoacetate or n-butyl acetoacetate; trimethylolpropane and methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate Tate or n-butyl acetoacetate reaction product; erythritol and methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate or n-butyl acetoacetate reaction product; pentaerythritol and methyl acetoacetate, ethyl acetoacetate , N-propyl acetoacetate or n-butyl acetoacetate reaction product; alkyl ketal ester corresponding to the reaction product of sorbitol and methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate or n-butyl acetoacetate Is included.

  Particular alkyl ketal esters include alkyl ketal esters having the following structures II-VI:

（式中、Ｒ^５は、メチル、エチル、ｎ−プロピルまたはｎ−ブチルである。Ｒ^５がメチルである時、この構造は、本明細書で「メチル−ＬＧＫ」または「Ｍｅ−ＬＧＫ」と称され、レブリン酸メチルとグリセリンとの反応生成物に相当する。メチル−ＬＧＫは、全比率において水と混和性がある。Ｒ^５がエチルである時、この構造は、本明細書で「エチル−ＬＧＫ」または「Ｅｔ−ＬＧＫ」と称され、レブリン酸エチルとグリセリンとの反応生成物に相当する。エチル−ＬＧＫは、全比率において水と混和性がある。エチル−ＬＧＫも、エチル−ＬＧＫ８０％に対して有機化合物が少なくとも２０％の程度まで、多数の疎水性および親水性の有機化合物に溶解するかまたはそれらと混和性がある。このような化合物の例として、メタノール、エタノール、テトラヒドロフラン、アセトン、酢酸エチル、ラウリン酸エチル、ラウリン酸、塩化エチレン、トルエン、酢酸、低分子量ポリ（プロピレングリコール）およびヒマシ油が挙げられる。Ｒ^５がｎ−プロピルである時、この構造は、本明細書で「ｎ−プロピル−ＬＧＫ」と称され、レブリン酸ｎ−プロピルとグリセリンとの反応生成物に相当する。ｎ−プロピル−ＬＧＫは、水９９％あたり約１％の程度まで水と混和性がある。Ｒ^５がｎ−ブチルである時、この構造は、本明細書で「ｎ−ブチル−ＬＧＫ」と称され、レブリン酸ｎ−ブチルとグリセリンとの反応生成物に相当する。ｎ−ブチル−ＬＧＫは、水９９％あたり約１％の程度まで水と混和性がある。これは、ｎ−ブチル−ＬＧＫ８０％に対して有機化合物が少なくとも２０％の程度まで、様々な有機化合物に溶解するか、またはそれらと混和性がある。このような有機化合物の例として、（エタノールおよび１，２−ブチレングリコールを含む）アルコール、（Ｃ_{１２〜１４}安息香酸アルキル、ミリスチン酸イソプロピルおよびパルミチン酸オクチルなどの）有機エステル、および（ヒマシ油、トウモロコシ油、大豆油およびヒマワリ油を含む）多くの植物油が挙げられる。）

Wherein R ⁵ is methyl, ethyl, n-propyl or n-butyl. When R ⁵ is methyl, this structure is referred to herein as “methyl-LGK” or “Me-LGK”. Which corresponds to the reaction product of methyl levulinate and glycerin.Methyl-LGK is miscible with water in all proportions. When R ⁵ is ethyl, this structure is referred to herein as “ethyl -LGK "or" Et-LGK ", corresponding to the reaction product of ethyl levulinate and glycerin, ethyl-LGK is miscible with water in all proportions, ethyl-LGK is also ethyl-LGK80 % Of organic compounds are soluble or miscible in a number of hydrophobic and hydrophilic organic compounds, to the extent of at least 20%. Ethanol, tetrahydrofuran, acetone, ethyl acetate, ethyl laurate, lauric acid, when ethylene chloride, toluene, acetic acid, low molecular weight poly (propylene glycol) and castor oil mentioned are .R ⁵ is n- propyl, this structure , Referred to herein as “n-propyl-LGK”, which corresponds to the reaction product of n-propyl levulinate and glycerin, which is about 1% per 99% water. When R ⁵ is n-butyl, this structure is referred to herein as “n-butyl-LGK” and corresponds to the reaction product of n-butyl levulinate and glycerin. N-Butyl-LGK is miscible with water to the extent of about 1% per 99% water, which means that at least organic compounds are at least 80% n-butyl-LGK. Soluble in or miscible with various organic compounds to the extent of 20% Examples of such organic compounds include alcohols (including ethanol and 1,2-butylene glycol), (C _{12- 14} organic esters such as alkyl benzoates, isopropyl myristate and octyl palmitate) and many vegetable oils (including castor oil, corn oil, soybean oil and sunflower oil).

（式中、Ｒ^１は、メチル、エチル、ｎ−プロピルまたはｎ−ブチルである。Ｒ^５がメチルである時、この構造は、本明細書で「メチル−ＬＰＫ」または「Ｍｅ−ＬＰＫ」と称され、レブリン酸メチルと１，２−プロピレングリコールとの反応生成物に相当する。Ｒ^５がエチルである時、この構造は、本明細書で「エチル−ＬＰＫ」または「Ｅｔ−ＬＰＫ」と称され、レブリン酸エチルと１，２−プロピレングリコールとの反応生成物に相当する。エチル−ＬＰＫは、水９７．５％に対して約２．５％の程度まで水と混和性がある。エチル−ＬＰＫも、エチル−ＬＰＫ８０％に対して有機化合物が少なくとも２０％の程度まで、親水性を変える様々な有機化合物に溶解するかまたはそれらと混和性がある。これらの化合物には、例えば、メタノール、エタノール、テトラヒドロフラン、アセトン、酢酸エチル、塩化メチレン、トルエン、シクロヘキサン、酢酸、低分子量ポリ（プロピレングリコール）、鉱油、ヒマシ油、菜種油、トウモロコシ油およびヒマワリ油が含まれる。

Where R ¹ is methyl, ethyl, n-propyl or n-butyl. When R ⁵ is methyl, this structure is referred to herein as “methyl-LPK” or “Me-LPK”. Which corresponds to the reaction product of methyl levulinate and 1,2-propylene glycol, when R ⁵ is ethyl, this structure is referred to herein as “ethyl-LPK” or “Et-LPK”. Which corresponds to the reaction product of ethyl levulinate and 1,2-propylene glycol Ethyl-LPK is miscible with water to the extent of about 2.5% with respect to 97.5% of water. Ethyl-LPK is also soluble or miscible in various organic compounds that change hydrophilicity to the extent that the organic compound is at least 20% relative to 80% ethyl-LPK. Meta Lumpur, ethanol, tetrahydrofuran, acetone, ethyl acetate, methylene chloride, toluene, cyclohexane, acetic acid, low molecular weight poly (propylene glycol), mineral oil, castor oil, rapeseed oil, includes corn oil and sunflower oil.

（式中、Ｒ^５は、メチル、エチル、ｎ−プロピルまたはｎ−ブチルである。Ｒ^５がエチルである時、この構造は、本明細書で「エチル−ＬＥＫ」または「Ｅｔ−ＬＥＫ」と称され、レブリン酸エチルと１，２−エチレングリコールとの反応生成物に相当する。エチル−ＬＥＫは、水９５％あたり約５％の程度まで水と混和性がある。）

(Wherein R ⁵ is methyl, ethyl, n-propyl or n-butyl. When R ⁵ is ethyl, this structure is referred to herein as “ethyl-LEK” or “Et-LEK”. And corresponds to the reaction product of ethyl levulinate and 1,2-ethylene glycol. Ethyl-LEK is miscible with water to the extent of about 5% per 95% water.)

（式中、Ｒ^５は、メチル、エチル、ｎ−プロピルまたはｎ−ブチルである。Ｒ^５がメチルである時、この構造は、本明細書で「メチル−ＡｃＡｃＧＫ」または「Ｍｅ−ＡｃＡｃＧＫ」と称され、メチルアセトアセテートとグリセリンとの反応生成物を表す。Ｒ^５がエチルである時、この構造は、本明細書で「エチル−ＡｃＡｃＧＫ」または「Ｅｔ−ＡｃＡｃＧＫ」と称され、エチルアセトアセテートとグリセリンとの反応生成物を表す。メチル−ＡｃＡｃＧＫとエチル−ＡｃＡｃＧＫの各々は、全比率において水と混和性がある。）

Where R ⁵ is methyl, ethyl, n-propyl or n-butyl. When R ⁵ is methyl, this structure is referred to herein as “methyl-AcAcGK” or “Me-AcAcGK”. And represents the reaction product of methyl acetoacetate and glycerin, when R ⁵ is ethyl, this structure is referred to herein as “ethyl-AcAcGK” or “Et-AcAcGK” and ethyl acetoacetate. Represents the reaction product of glycerin and methyl-AcAcGK and ethyl-AcAcGK are miscible with water in all proportions.)

（式中、Ｒ^５はメチル、エチル、ｎ−プロピルまたはｎ−ブチルであり、Ｒ^６はメチルまたはエチルである。構造ＶＩによる化合物は、トリメチロールエタン（Ｒ^６＝メチル）またはトリメチロールプロパン（Ｒ^６＝エチル）とレブリン酸のＣ_１〜４エステルの反応生成物に相当する。）

Wherein R ⁵ is methyl, ethyl, n-propyl or n-butyl and R ⁶ is methyl or ethyl. Compounds according to structure VI are trimethylolethane (R ⁶ = methyl) or trimethylolpropane ( R ⁶ = ethyl) and the reaction product of C _1-4 ester of levulinic acid.)

  The alkyl ketal esters of the present invention can be prepared by reaction of alkyl esters of oxocarboxylates with aliphatic polyol compounds, which aliphatic polyol compounds (as well as 1,2-diols) are adjacent aliphatic It has hydroxyl groups on carbon atoms or on aliphatic carbons separated from each other by one carbon atom (similar to 1,3-diol). When the starting polyol compound has a hydroxyl group (on an adjacent carbon atom) that reacts with a ketoester or semialdehyde ester, b in structure I is 0. When a ketoester or semialdehyde ester reacts with a hydroxyl group on a carbon atom separated by another carbon atom, b in structure I is 1. This reaction may be carried out in the presence of an acid catalyst. A preferred process is described in WO 09/032905.

Suitable and suitable oxocarboxylates for making alkyl ketal esters include both ketoesters and semialdehyde esters. “Ketoester” refers to a compound having at least one ketone moiety and one carboxylic ester moiety. The compound may have two or more ketone groups or two or more carboxylic ester groups. “Semialdehyde ester” refers to a compound having at least one aldehyde group and one carboxylic ester group. The compound may have two or more aldehyde groups or two or more carboxylic ester groups. In each case, the ester group is a lower alkyl group corresponding to the R ⁵ group of structure I.

  The ketoester or semialdehyde ester is not particularly limited with respect to the additional moieties or functional groups present in addition to the ketone or aldehyde group and the carboxylic ester group. In some embodiments, the compound includes one or more halogen groups, carbonate groups, carboxylic acid groups, carboxylic ester groups, sulfone groups, imide groups, amide groups, amine groups, mercapto groups, protected thiols. Groups, protected hydroxyl groups, ether groups, disulfide groups, phosphate groups, phosphonooxy groups, siloxane groups, silyl groups, or silane groups may be included. In addition, keto acid esters or semialdehyde acid esters are protected, for example, provided that they are protected by one or more trimethylsilyl or t-butyl groups, or one or more other protecting groups known to those skilled in the art. , Hydroxyl groups or mercapto groups may be included.

Some examples of suitable ketoesters include pyruvic acid, acetoacetic acid, levulinic acid, 5-aminolevulinic acid, oxaloacetic acid, α-ketobutyric acid, α-ketoglutaric acid, α-ketoisovaleric acid, 5-ketohexanoic acid, α- Ketoisocaproic acid, α-ketoadipic acid, 3-ketoadipic acid, 2-keto-4-methylthiobutyric acid, 4-acetylbutyric acid, 2-keto-3-bromobutyric acid, phenylpyruvic acid, 2-keto-3-phenylpropanoic acid, 2-ketopentanoic acid, 3-ketohexanoic acid, 4-ketohexanoic acid, 2-ketooctanoic acid, 3-ketooctanoic acid, 4-ketooctanoic acid, 7-ketooctanoic acid, 2-keto-4-pentanoic acid, 13-keto-9, 11-octadecadienoic acid, 4-ketostearic acid, 9-ketopalmitic acid, 4-ketoheptanedioic acid, penicillic acid, 8- Such as keto-8-aminopelargonic acid, 2-keto-5-aminovaleric acid, 2-succinylamino-6-oxoheptanedioic acid, 2-oxo-3-butinoate, 3-keto-6-acetamidohexanoate C ₁ -C ₄ alkyl esters.

In a preferred embodiment, the keto ester is _C 1 -C ₄ alkyl esters of levulinic acid (4-oxopentanoic acid). Levulinic acid is an abundant raw material prepared on an industrial scale from pentose, hexose and polysaccharides including pentose and hexose, such as cellulose, hemicellulose, starch, sucrose. Other preferred ketoethers include C ₁ -C ₄ alkyl esters of pyruvic acid and acetoacetic acid. Particularly preferred ketoesters include ethyl levulinate, n-propyl levulinate and n-butyl levulinate.

Some examples of suitable semialdehyde esters include aspartic acid semialdehyde, 4-oxobutanoic acid, 5-oxopentanoic acid, 6-oxohexanoic acid, 7-oxoheptanoic acid, α-formylglycine, 3-oxo-2 -(Phosphonooxy) -propanoic acid (tartronic acid semialdehyde in which the hydroxyl group is protected by phosphate) 3-oxopropanoic acid (malonic acid semialdehyde), 2-methyl-3-oxopropanoic acid (methylmalonic acid semialdehyde) Aldehyde), succinic semialdehyde, adipic acid semialdehyde, 5-glutamyl semialdehyde, allicin, 2-aminomuconic acid semialdehyde, 4-amino-5-oxopentanoic acid, N-acetylglutamic acid semialdehyde, 2-amino-3 -(3-Oxoprop-1-ene ) - but-2-ene diacid, and N-2- _C 1 ~C ₄ alkyl esters of succinyl -L- glutamic acid-5-semialdehyde and the like. For other semialdehyde esters, ozonolysis of unsaturated fatty acid esters is performed to form an aldehyde moiety at the unsaturated site, as described in Criegee, Angew. Chem. Int. Ed., 1975, 87,745. C ₁ -C ₄ alkyl esters of semialdehyde compounds formed by

The polyol used to form the alkyl ketal ester may contain one or more heteroatoms in addition to the hydroxyl group. When present, these heteroatoms form substituents on the R ² , R ³ and / or R ⁴ moieties of structure I. These one or more heteroatoms may be present in the form of one or more additional functional groups including, for example, halogen, sulfone, imide, amide, mercapto, ether, disulfide, phosphate , Phosphonooxy, siloxane, silyl, or silane. The diol may contain additional hydroxyl or thiol groups. Suitable alkanediols include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neo Pentyl glycol), 3-mercaptopropane-1,2-diol (thioglycerol), dithiothreitol, 1,2-butanediol, 1,3-butanediol, cyclohexane-1,2-diol, 1,4-dioxane -2,3-diol, 3-butene-1,2-diol, indan-1,2-diol, tartaric acid, and 2,3-dihydroxyisovaleric acid are included. In some embodiments, alkanediols are synthesized by epoxidation of n-α-olefins such as 1-octene, 1-hexene, 1-decene, followed by ring opening to form the diol. Preferred polyols include 1,2-propanediol, 1,3-propanediol and 1,2-ethanediol, glycerin, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol and sorbitol.

  Particular embodiments of the present invention include a co-solvent mixture comprising water and at least one alkyl ketal ester. This co-solvent mixture is a clear, homogeneous solution in the absence of other substances. The at least one alkyl ketal ester in the cosolvent mixture should itself be miscible with water in the relative proportions of water and alkyl ketal ester present in the solution. As defined above, this co-solvent mixture preferably comprises at least one highly water miscible alkyl ketal ester. This co-solvent mixture may contain two or more alkyl ketal esters, in which case at least one of them is itself miscible with water in the relative proportion of water and alkyl ketal ester present. There should be. In some embodiments, both the highly water miscible alkyl ketal ester and the slightly less water miscible alkyl ketal ester are present in the co-solvent mixture.

  In some embodiments, the co-solvent mixture is based on the combined weight of water, alkyl ketal ester (s) that may be present, and any additional highly water miscible solvent (s). At least 5% by weight of water. In other embodiments, the co-solvent mixture may comprise at least 10 wt% water, at least 25 wt% water, or at least 50 wt% water on the same basis. In some embodiments, on the same basis again, it may contain as much as 99 wt% water, or as much as 75 wt% water.

  Additional water miscible solvent (s) may be present in such co-solvent mixtures. These highly water miscible solvent (s) should have a molecular weight of 250 or less, preferably 150 or less, more preferably 120 or less. A water miscible solvent having a molecular weight of 120 or less is considered a “volatile organic compound” for the purposes of the present invention. Additional examples of such highly miscible solvents include, for example, lower alcohols such as methanol, ethanol, n-propanol and isopropanol; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propane Glycols and glycol ethers such as diols, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether; formaldehyde, acetaldehyde, acetone and methyl ethyl ketone If aldehyde such as Esters such as ethyl lactate, and other organic compounds such as certain chlorinated solvents, as well as its high own water miscible dimethyl isosorbide; ketone.

  The co-solvent mixture according to one aspect of the present invention is an excellent solvent for a wide range of materials, including a wide range of organic materials that are slightly less miscible with water. It is the present invention that solutions of many organic materials with low solubility can be made into aqueous based solvent systems that contain little or no volatile organic chemicals, especially organic chemicals having a molecular weight of less than 100. This is an advantage of this aspect. The solute concentration in the co-solvent system is often much higher than the concentration that can be obtained in water alone.

  A wide range of materials can form solutes in this aspect of the invention. The solute in some embodiments is an organic compound or comprises an organic compound. Since this co-solvent mixture is often a better solvent for such organic compounds than water alone, organic compounds that are of particular interest as solutes have no or very limited miscibility with water. It is a compound. In many cases, this solute has a solubility of only 5% per 95% water, only 2% per 98% water, or only 1% per 99% water. In some embodiments, the solute may include two or more organic compounds.

  This solute must dissolve to some extent in at least one alkyl ketal ester present in the cosolvent mixture. It is preferred that the co-solvent mixture is itself soluble to the extent of at least 10% per 90% by weight of at least one alkyl ketal ester. More preferably, the solute is dissolved in the solvent mixture to the extent of at least 20% per 80% by weight of the at least one alkyl ketal ester. The alkyl ketal ester is miscible with the alkyl ketal ester to the extent of at least 50% per 50% by weight, or to the extent of 80% per 20% by weight of the alkyl ketal ester, or miscible with the alkyl ketal ester in all proportions. There may be sex.

  One class of solutes are the low-solubility alkyl ketal ester (s), especially the low-solubility alkyl ketal esters that are miscible with water to the extent of only 5% per 95% water. Accordingly, in some embodiments, the solution of the present invention is a solution comprising water, a highly water miscible alkyl ketal ester, and a slightly less water soluble alkyl ketal ester. In these embodiments, the slightly less water-soluble alkyl ketal ester may be present at a concentration higher than the solubility limit in water alone. This slightly miscible alkyl ketal ester may be a functional component of a composition such as a cleaning agent that provides a specific cleaning function such as, for example, degreasing. This slightly miscible alkyl ketal ester is intended to solubilize or emulsify further constituents that do not dissolve or easily disperse in either water or the first water miscible alkyl ketal ester. Can also help.

Another class of solutes are surfactants, which can be nonionic, cationic, anionic or zwitterionic types of surfactants. Surfactants useful herein include known anionic synthetic surfactants, nonionic synthetic surfactants, amphoteric synthetic surfactants and zwitterionic synthetic surfactants. Suitable surfactants summarized in detail are McCutcheon's EMULSIFIERS
AND DETERGENTS, North American Edition, 1984, McCutcheon Division, MC Publishing Company, which is incorporated herein by reference. Typical examples of these include alkylbenzene sulfonates, alkyl sulfonates and alkyl ether sulfonates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkylphenols, alkylpolyglucosides. , Isethionic acids, amides of long chain fatty acids (such as various cocamide surfactants, lauric acid amide surfactants); various tartaric acids, amine oxides, alpha-sulfonates of fatty acids and fatty acid esters, alkylbetaines Fluorinated hydrocarbon surfactants (especially anionic surfactants), sulfosuccinates and the like, which are well known in the technical field of surface activity. Generally, such detergent surfactants contain _C9-18 alkyl groups. Anionic detergent surfactants can be used in the form of their sodium, potassium or triethanolammonium salts. These nonionic detergent surfactants generally contain from about 5 to about 17 ethylene oxide groups. C _11-16 alkyl benzene sulfonates, C _12-18 paraffin sulfonates and alkyl sulfonates, alkyl polyglucosides, and ethoxylated alcohols and alkyl phenols are particularly preferred for compositions of the type of the present invention. If the surfactant is present as a solute, its concentration is below the critical micelle concentration of the surfactant in the particular co-solvent mixture. It is an advantage of the present invention that when the surfactant is a solute, a higher concentration of surfactant can often be dissolved in this co-solvent mixture than can be dissolved only in water. .

  Other types of low water-soluble organic compounds that can serve as solutes include linear, branched, or cyclic aliphatic hydrocarbons having up to about 30 carbon atoms; 2-20 Α-olefins having the following carbon atoms and a boiling point of at least 100 ° C .; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclobutane, and cyclopentadiene; aromatic compounds such as benzene and naphthalene; alkyl Monoalkylbenzene or polyalkylbenzene, each of the group (s) containing 1 to 12 carbon atoms, preferably 6 to 9 carbon atoms; methylene chloride, chloroform, 1,2-dichloroethane, 1,1-dichloroethane Alkane chlorides such as ethyl chloride; brominated alkanes such as chlorobromomethane, methylene bromide and bromoform Down like; as well as include esters such as amyl acetate, and the like.

  Other less water-soluble organic compounds that can serve as solutes include (but are not limited to, vegetable oils, animal fats, mineral oils, silicone oils, and natural oil derivatives such as fatty acid methyl esters). ) Various terpenes and various natural and synthetic oils are included.

  Various glycol ethers and glycol ether acetates with low water solubility are also useful as solutes, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, propylene glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol n-butyl ether Including but not limited to acetate and the like.

  The solute may also include one or more esters, ketones, or amides, one or more fragrances or dyes; substances such as α-glucose pyranose compounds; or enzymes such as proteases and amylases.

  In the solution of the present invention, the solute is present in an amount below the solubility limit of the cosolvent mixture so that the combination of the cosolvent mixture and solute forms a clear solution. In some embodiments, the concentration of the solute is higher than the concentration that can itself dissolve in water. Other ingredients that are not dissolved in the solution of the present invention can result in a formulation that includes a solution that is cloudy or forms an emulsion.

  In another embodiment of the invention, the co-solvent mixture comprising water and a water miscible alkyl ketal ester forms a continuous or co-continuous phase in the emulsion. The physical form of such emulsions can range from slightly turbid, low viscosity liquids to very opaque pasty semisolid materials, depending on the specific components present in the emulsion and their relative proportions. . The dispersed phase or second co-continuous phase does not mix with the co-solvent mixture forming the continuous phase or other co-continuous phases in the proportions present. In these emulsions, the alkyl ketal ester often provides some degree of compatibilization between these phases, which can form a more highly stable emulsion by inhibiting layer separation. it can. Better emulsion stability is manifested by greater resistance to layer separation and / or the ability of the dispersed or co-continuous phase to resist layer separation over a wider range of temperatures than when no alkyl ketal ester is present Can be. In some cases, the alkyl ketal ester is partitioned between the continuous and dispersed phases, or between the co-continuous phases.

  The dispersed phase or second co-continuous phase is one or more organic substances or mixtures or organic substances (not mixed with the co-solvent mixture forming the continuous phase or the first co-continuous phase) or co-solvents The mixture may be somewhat miscible (less soluble) but nevertheless may be an organic substance or mixture thereof present in an amount exceeding its miscibility limit in the co-solvent mixture.

  Therefore, any of the potential solute materials described above that are not miscible with this co-solvent mixture can form all or part of the dispersed or co-continuous phase of the emulsion of the present invention.

  In another aspect, the present invention is a composition comprising at least one alkyl ketal ester of structure I and at least one surfactant. As mentioned above, the composition of this aspect of the invention may take any of several forms including various solutions and emulsions. The composition of this aspect of the invention is often used in a variety of formulated cleaning compositions. In cleaning compositions, these surfactants can provide the usual cleaning and emulsifying benefits associated with the use of such materials. Surfactants useful herein include anionic surfactants, nonionic surfactants, amphoteric surfactants and zwitterionic surfactants described herein.

  The surfactant may comprise as little as 0.1% of the composition of this aspect of the invention, but generally the composition comprises 1-75% surfactant, preferably 1-40. %, And more preferably 1-20%. In some embodiments, a composition comprising a surfactant and an alkyl ketal ester may take the form of a concentrated formulation and is designed to be diluted when used. Such concentrated formulations typically contain only 60% of a combination of water and / or volatile organic compounds, and more typically contain only 40%. Such concentrated formulations may contain 5 to 70% or 10 to 50% by weight of at least one alkyl ketal ester and 5 to 70% or 10 to 50% by weight of at least one surfactant. Many. When the product is made dilutable in water, the alkyl ketal ester in such a concentrated formulation is at least one highly water miscible alkyl ketal ester or at least one highly water miscible alkyl ketal ester. It is preferable to include a mixture of a ketal ester and an alkyl ketal ester having low water solubility. However, this concentrated product may contain only alkyl ketal esters with low water solubility.

  The surfactant / alkyl ketal ester compositions of the present invention may be formulated into clear liquids, various types of emulsions, and solid forms such as granules, tablets or bars. These compositions may be incorporated into absorbent materials such as wipes, brushes and sponges.

  The cleaning compositions of the present invention contain various additional ingredients (in addition to surfactants and alkyl ketal esters) and perform specific functions for special cleaning applications. Some examples of such ingredients include, for example, water, cleaning builders and / or chelating agents, chlorinated bleach, non-chlorine bleach, bleach activator, bleach stabilizer, soil suspension, hydrotrope , Organic solvents with high water miscibility, organic solvents with low water solubility, oils and oil derivatives, abrasives, antibacterial agents, colorants, inorganic salts, thickeners, enzymes, sprays, pH adjusters, Examples include, but are not limited to, additives such as fabric softeners, metal peroxides and emollients.

Cleaning builders are generally present in laundry detergents, hard surface cleaning products and dishwashing liquids and may be present in the cleaning compositions of the present invention. Examples of such builders include N-diethylene glycol-N, N-diacetic acid (DIDA) polyphosphate (eg, potassium pyrophosphate), nitrilotriacetate (eg, Na ₃ NTA), sodium ethylenediaminetetraacetate (EDTA). ), Ethylene triamine sodium pentaacetate, sodium citrate, sodium carbonate, sodium metasilicate and zeolites (eg, zeolites having a cation exchange capacity of 200 mg or more (calculated as CaCO ₃ ) per gram of zeolite). Enzymes such as proteases and amylases are also frequently present in cleaning compositions, particularly laundry detergent products and prewash products.

  The cleaning composition of the present invention comprises bleaching agents such as sodium hypochlorite, sodium perborate, diperoxide decanedioic acid, sodium dichloroisocyanurate, m-chloroperoxybenzoic acid and peroxide based bleaching agents. But you can. It is an advantage of the present invention that this alkyl ketal ester is stable in a bleaching solution and, therefore, excellent solubility in oily soils can be added to a composition containing a bleaching agent. The composition comprising the bleach of the present invention may also comprise one or more bleach activators such as tetraacetylethylenediamine and sodium nonanoyloxybenzenesulfonate.

  The cleaning composition of the present invention comprises one or more soil suspending agents such as carboxymethylcellulose sodium; one or more bleach stabilizers such as diethylenetriaminepentamethylenephosphonate and sodium diethylenetriaminopentaacetate; sodium toluenesulfonate One or more hydrotropes such as sodium cumene sulfonate and potassium xylene sulfonate; and one or more fabric softening ingredients such as smectite clay and tallow dimethylammonium chloride.

  The cleaning composition of the present invention may contain the above-described highly miscible organic solvent.

  The cleaning composition of the present invention may include one or more slightly miscible organic solvents including a so-called “degreasing” type of solvent that is often incorporated into cleaning agents to remove oily soils. The alkyl ketal esters often can replace those organic solvents in the cleaning formulation or reduce the amount that is required. In certain embodiments, it is an advantage of the present invention that the alkyl ketal ester often serves to solubilize or disperse such materials in the aqueous phase. This may allow large amounts of such solvents to be incorporated into cleaning formulations while maintaining stability against phase separation. In other embodiments, better stability of the solution or emulsion can be obtained in such a solution or emulsion at a given concentration of organic solvent.

Examples of these low miscible organic solvents include benzyl alcohol, n-hexanol, certain alcohols such as 2,2,4-trimethyl-1,3-pentanediol, and terpenoids such as menthol, terpineol, borneol, geraniol Is mentioned. Further examples include various low water solubility such as dipropylene glycol monobutyl ether, monopropylene glycol monobutyl ether, diethylene glycol monohexyl ether, monoethylene glycol monohexyl ether, butoxypropanol, butoxypropoxypropanol, diethylene glycol monobutyl ether and mixtures thereof. A glycol ether is mentioned. Hydrocarbons or halogenated hydrocarbons of the alkyl or cycloalkyl type and whose boiling point is well above room temperature, ie above about 20 ° C., are generally used as degreasing solvents that may be present in the cleaning compositions of the present invention. . Among these are terpenes and terpene oxides such as dipentene, pinene, d-limonene, 1-limonene, limonene oxide, myrcene. Additional compounds with low miscibility with water that may be present include C _6-9 alkyl aromatic solvents, especially C _6-9 alkyl benzenes, preferably octyl benzene. They exhibit excellent properties for removing fats and oils and tend to have a low level of pleasant aroma. Olefins having a boiling point of at least about 100 ° C., in particular α-olefins such as 1-decene or 1-dodecene, are also excellent solvents for removing fats and oils.

  Both natural and synthetic oils and their derivatives may be present in the cleaning compositions of the present invention. They may function as oil-based cleaning agents, as solvents for certain types of soils, as rheology modifiers, as lubricants, and in some cases may impart a pleasant scent to the composition. Such soils include, but are not limited to, mineral oil and various types of vegetable and vegetable oils (including both natural and improved vegetable oils). Pine oil is a famous example of a vegetable oil useful in cleaning compositions. In some embodiments, oil derivatives such as fatty acid esters may be used in the cleaning composition.

  The cleaning composition of the present invention may include one or more abrasives such as, but not limited to, silica, pumice, calcium carbonate, polyvinyl chloride, and perlite. It may contain other dissolved inorganic salts such as sodium sulfate, sodium chloride (which can function as a viscosity modifier, flow regulator or pH buffer). It may contain beauty enhancing ingredients such as dyes and perfumes, as well as various excipients. Sodium and potassium soaps, especially coconut soap, can be included, especially when used in creams.

  In addition to the foregoing, the compositions of the present invention may include other additives such as metal peroxides and emollients.

  The presence of an alkyl ketal ester can provide several benefits to the cleaning composition. These alkyl ketal esters have low volatility and are non-corrosive chemicals. Furthermore, the cleaning compositions according to the present invention are effective against various soils and / or stains and can be formulated for use with various substrates. These alkyl ketal esters often serve a function that helps solubilize and compatibilize, resulting in cleaning compositions having excellent resistance to phase separation. The alkyl ketal ester can also reduce the amount of other ingredients required for the formulation, such as surfactants and other solvents. In some cases, one or more of these other components can be completely removed.

  One class of cleaning compositions of the present invention includes hard surface cleaners that can be utilized for industrial, facility, office, or home use. These include, for example, versatile hard surface cleaners, toilet cleaners, shower / bath / tile cleaners, disinfectants, soap residue removers, mildew removers, glass / mirror cleaners or stains. It may be formulated as a release agent. Many of these cleaning agents are formulated as dilute solutions or emulsions, and many are applied by spray.

  Hard surface cleaners according to the present invention can in most cases contain water comprising at least 20% by weight of the total composition. In some embodiments, water can comprise at least 50% by weight of the total composition and may comprise at least as much as 99% by weight of the total composition. In some embodiments, the hard surface cleaner further comprises an alkyl ketal ester that is highly water miscible, preferably an alkyl ketal ester that is miscible with water in all proportions. Examples of such highly water miscible alkyl ketal esters include Me-LGK, MeAcAcGK, Et-AcAcGK, or, in particular, Et-LGK, but it is possible to use a mixture of two or more alkyl ketal esters. it can. In some embodiments, the highly water miscible alkyl ketal ester (s) may be present in conjunction with a slightly less water miscible alkyl ketal ester. Examples of alkyl ketal esters with slightly lower water miscibility include n-propyl-LGK, n-butyl-LGK, ethyl-LPK and ethyl-LEK. In some embodiments, the alkyl ketal ester (s) may be present in an amount up to 50% by weight of the hard surface cleaner. The amount of alkyl ketal ester present in the hard surface cleaning composition is about 1% to about 50% by weight of the total composition, preferably about 1% to about 20% by weight of the total composition, more preferably It may be about 3% to about 15% by weight of the total composition, or about 2% to about 10% by weight of the total composition.

In some embodiments, the hard surface cleaner may comprise only water and the alkyl ketal ester (s) described herein. In some embodiments, the hard surface cleaner may further comprise a fragrance and / or a dye. In these cases, the alkyl ketal ester function may be the function of a soil release agent, or more generally as an active cleaning agent. More typically, the hard surface cleaner includes an additional functional material, and in most cases includes at least one surfactant. In the hard surface cleaner comprising both the alkyl ketal ester and the surfactant, the alkyl ketal ester (s) comprise (a) a function to solubilize and emulsify the surfactant and (b) an active detergent. It may perform any or all of several functions such as The surfactant in these hard surface cleaners may be an anionic surfactant or a mixture of one or more anionic surfactants and one or more nonionic surfactants. Many. Alternatively (or in addition), the surfactant may comprise one or more substances derived from a plant source such as one or more C _10-16 alkyl glycosides, alkyl betaines, or sulfosuccinates.

In certain embodiments, the hard surface cleaning formulation may include the following as a percentage of the total formulation weight:
a) Water: 20-99%, more typically 50-95%;
b-1) One or more highly water miscible alkyl ketal ester (s): 0 to 25%, more typically 1 to 10%, the alkyl ketal ester is Me-LGK, Me -Preferably comprises at least one of AcAcGK, Et-AcAcGK or Et-LGK;
b-2) one or more slightly miscible alkyl ketal ester (s): 0-10%, more typically 0-5%; this alkyl ketal ester is at least one of b) and c) Preferably comprises at least one of n-propyl-LGK, n-butyl-LGK, ethyl LPK and ethyl-LEK, provided that one is present;
c) One or more surfactant (s): 0.01% -20%, preferably 0.1-15%, more preferably 0.25-10%, even more preferably 1-7 %, Optionally 1-5%; the surfactant (s) are (1) at least one anionic surfactant, (2) at least one nonionic surfactant, ( 3) a mixture or nonionic surfactant of at least one nonionic surfactant and at least one anionic surfactant; (4) a C _10-16 alkyl glycoside, alkylbetaine or sulfosuccinate One or more of them, or (4) (1), (2) or a mixture of (3) and (4) is preferred;
d) one or more propellants which are generally low-boiling hydrocarbons such as butane, pentane, hexane and cyclohexane or chlorinated hydrocarbons and / or fluorinated hydrocarbons having a boiling point of −10 ° C. to 50 ° C .;
e) One or more organic miscible solvent (s) with slightly lower water miscibility; generally 0-10%, preferably 0.1-5%, if present. This includes, for example, the above-mentioned long chain alcohols, glycol ethers, hydrocarbons, halogenated hydrocarbons, C _6-9 alkyl aromatic compounds, olefins, terpenes, terpene oxides, terpenoids, oils Or one or more of natural oil derivatives;
f) One or more highly water miscible organic solvents such as lower alcohols (eg, ethanol and 1-propanol), acetone, goricols, and glycol ethers: 0-10%, preferably 0 if present .1-5%;
g) 1 or more antimicrobial agents, 0 to 5%, preferably, if present, 0.1% to 2%, as some _{examples, C 12-16} quaternary ammonium chloride such as alkyl dimethyl benzyl ammonium chloride And various phenylphenol compounds;
h) one or more builders or chelating agents, especially chelating agents such as phosphate, citrate, ETDA, or DIDA: 0-30%, preferably 0.05-10%, if present Preferably, if present, 0.5-1%, even more preferably 2-8%, if present, and even more preferably 2-6%, if present;
i) One or more bleaches including, for example, a chlorine bleach such as sodium hypochlorite, or a non-chlorine bleach such as hydrogen peroxide or other peroxy compounds: 0-10%, preferably present If 0.1 to 5%;
j) one or more pH adjusting agent (s) (eg acid, base, pH buffering agent): 0-2%, preferably, 0.05-1% if present;
k) one or more dyes: 0-5%, preferably 0.1-2%, if present;
l) one or more water-soluble inorganic salts such as sodium sulfate: 0-10%, preferably 0.1-5%, if present;
m) For example, one or more viscosity thickeners comprising a water soluble polymer; 0-10%, preferably 0.1-5% if present;
n) one or more proteolytic enzymes, 0-5%: preferably 0.1-1%, if present;
o) one or more abrasives; and p) one or more fragrances.

  The above components b-2) and d) to p) may be present in any combination of any two or more thereof. Mixtures of any or all of components b-2) and e) -n) provided that some of component b-1) must be present if component b-2) is not present May be excluded in any particular hard surface cleaning formulation. Component d) is typically present in spray cleaning formulations. It is readily noticed that in some cases a single substance may perform multiple functions in a hard cleaning formulation.

  Component j) is often present to provide a pH of 3.5 or higher, preferably 6-10.

  Some exemplary hard cleaning formulations according to the present invention are as follows. The percentages shown are weight percent based on the total formulation weight. In these hard cleaning preparations, the alkyl ketal ester preferably contains at least one component b-1) substance such as ethyl-LGK, methyl-LGK, methyl-AcAcGK and ethyl-AcAcGK. . These hard cleaning formulations may comprise one or more constituents b-1) substances, one or more constituents b-2) substances, for example methyl-LPK, ethyl-LPK, ethyl LEK, It may include n-propyl-LGK, n-butyl-LGK, etc., or a mixture of b-1) and b-2 materials. Depending on the specific formulation, the function of the alkyl ketal ester in these formulations is (1) decomposition and / or removal of soil; (2) compatibilization of components, especially components with low water solubility, into water; (3) 1 One or more of the formation of a co-solvent mixture in which more than one type of other components are dissolved or dispersed, and (4) removal or reduction of surfactants and / or organic solvents or others may be included.

General preparation 1-Aqueous detergent for tile in shower room Anionic detergent 0-10%
Alkyl ketal ester 1-10%
Propylene glycol butyl ether 0-10%
D-glucopyranose, oligomer, decyloctyl glycoside 0-10%
D-glucopyranose, oligomer, C _10-16 alkyl glycoside 0-10%
Builder (s) 0-5%
Antibacterial agent (orthophenylphenol sodium) 0-5%, preferably 0.1-5%
Water (balance of this formulation)

  At least one of these surfactants (one of an anionic surfactant and / or an alkyl glycoside) is present in the above formulation. The total surfactant level is generally in the range of 1 to 10% by weight.

General Formulation 2-Aqueous Pine Cleaner Lower Alkanol 0-10%
Alkyl ketal ester 0.1-25%
Pine oil 0.1-10%
Bactericides (eg, quaternary alkyl (C _12-16 ) dimethylbenzylammonium chloride) 0-5, preferably 1-5%
Nonionic and / or amphoteric surfactants 1-15, preferably 1-5%
Water (balance of this formulation)

  This alkyl ketal ester and water are believed to form a co-solvent mixture in formulations where either the lower alkanol (if not present in the formulation), pine oil and surfactant are either dissolved or dispersed. Yes. The presence of this alkyl ketal ester can make it possible to reduce or eliminate lower alkanols as well as reduce or eliminate the amount of pine oil.

General preparation 3-Aqueous release agent for soap ground Surfactant 1-10%
Diethylene glycol monobutyl ether 0-10%
Chelating agent (for example, EDTA tetrapotassium salt) 1-10%
Builder (eg, sodium carbonate) 0-2%
Alkyl ketal ester 0.1-10%
Water (balance of this formulation)

  The alkyl ketal ester and water can form a co-solvent mixture in the formulation in which diethylene glycol monobutyl ether (if present in the formulation) and surfactant are dissolved. In the presence of this alkyl ketal ester, it may be possible to reduce or eliminate the amount of diethylene glycol monobutyl ether.

General preparation 4-Aqueous detergent for toilet bowl Alkyl ketal ester 1-10%
Sodium hydroxide 0 to <1%, preferably 0.1 to <1
Amine oxide type surfactant 0- <5%, preferably 0.1- <5
Sodium hypochlorite 0- <5%, preferably 0.1- <5
Water (balance of this formulation)

  This alkyl ketal ester functions in the formulation as a chelating agent and is believed to help solubilize or emulsify other ingredients.

General Formulation 5-Aqueous Detergent for Hard Surface 0.1 to 27% Mixture of Alkyl Ketal Ester with High Water Miscibility and Slightly Miscibility
Sodium xylene sulfonate 0- <2%, preferably 0.1- <2
d-limonene 0 ~ <2%
Polyethylene glycol (5) undecyl ether 0 to <2%, preferably 0.1 to <2.
Ethoxylated C _8-16 alkyloxypropanamine 0 to <2%, preferably 0.1 to <2.
Water (balance of this formulation)

  d-Limonene is often used as a degreasing solvent in hard surface cleaners. The alkyl ketal ester can replace d-limonene in the formulation or reduce the amount of d-limonene. This can also solubilize or emulsify d-limonene so that, if desired, d-limonene can be present in high concentrations. When performing the degreasing function in this formulation, this cleansing formulation contains 0.1-25% of an alkyl ketal ester that is slightly less soluble (generally a stronger oil-based cleaner than a highly water miscible type). May be included. This highly water miscible alkyl ketal ester may contain up to 20% of this formulation and tends to function as a compatibilizing and / or solubilizing agent for other ingredients including slightly less water miscible alkyl ketal esters. There is.

General preparation 6-Aqueous detergent for glass Lower alcohol 0-7%
Surfactant 0.5-3%
2-Butoxyethanol 0-5%
Alkyl ketal ester 1-10%
Water (balance of all preparations)

  The alkyl ketal ester and water can form a co-solvent mixture in the formulation in which the lower alcohol and 2-butoxyethanol (if present) are solubilized or dispersed. In some formulations, the alkyl ketal ester can replace both lower alcohols and 2-butoxyethanol.

General Formulation 7-General Cleaning Formulation Water At least 60%
Nonionic surfactant (s) 0-35, preferably 0.15-35%
Anionic surfactant 0-10, preferably 0.05-10%
Alkyl ketal ester 0.1-25%
Water-soluble organic solvent 0-20%
0.1-5 salt, preferably 0.1-2%

  In particular, if a degreasing function is required, an alkyl ketal ester with slightly low water miscibility can be used, but an alkyl ketal ester with high water miscibility is preferred for this formulation.

General preparation 8-d-limonene detergent d-limonene 1-60%
10-30% surfactant
20-65% water
Alkyl ketal ester 0.1-10%
Additive 2-12%

  The cleaning formulation can include a mixture of a highly water miscible alkyl ketal ester and a slightly less water miscible alkyl ketal ester, a highly water miscible alkyl ketal ester alone, or a mixture of both types. The presence of these alkyl ketal esters in the formulation makes it possible to reduce the level of d-limonene (especially when there is a slightly less water miscible alkyl ketal ester), allowing d-limonene in the aqueous phase. It can be solubilized or emulsified.

General Formulation 9-Aqueous Spot Remover Sodium Hydroxide 0.5-1.5%
Acrylic acid polymer / copolymer 1-5%
C _12-14 secondary ethoxylated alcohol 0-13%
Alkyl ketal ester 0.1-25%
75-90% water

General Formulation 10—Aqueous Foaming Cleaner Chelating Agent (eg, Ethylenediaminetetraacetic acid tetrasodium) 3-7%
Isobutane 3-7%
Diethylene glycol monobutyl ether 0-7%
Alkyl ketal ester 0.1-10%
Anionic surfactant 1-10
Nonionic surfactant 0-5
Water (balance of this formulation)

General Formulation 11-Floor Cleaner Propylene Glycol Monomethyl Ether 0-15%
Alkyl ketal ester with high water miscibility 0.1-25%
55-61% water
Oleic acid 0-17%
Alkyl ketal ester with slightly low water miscibility 0.1-25%
Triethanolamine 11-13%

General Formulation 12-Floor Release Agent I
Propylene glycol monomethyl ether 0-15%
Alkyl ketal ester with high water miscibility 0.1-25%
Ammonium hydroxide 0-10, preferably 1-7%
Anionic surfactant (for example, sodium ethylhexyl sulfate) 4-5%
Water (balance of all preparations)

  The alkyl ketal ester (s) of General Formulations 11 and 12 can serve the function of breaking down oil stains and removing other stains in this formulation, with the removal or further complete removal of propylene glycol monomethyl ether. Could be possible.

General Formulation 13-Floor Release Agent II
Surfactant (anionic / nonionic) 1-20%
Thickener 0-5%
Alkali or alkanolamine 1-40%
Highly water miscible alkyl ketal ester 0.1-40%
Water (balance of all preparations)

  Any of the hard surface cleaners described above, including the hard surface cleaners of General Formulations 1-13, reduce the amount of water, thereby at least the surfactant concentration, preferably the alkyl ketal ester. And can be prepared in concentrated form by increasing the concentration of both surfactant and surfactant. Such concentrated hard surface cleaning formulations may contain up to 60% of the combination of water and / or volatile organic mixture, more typically only 40%. Such concentrated formulations comprise 5 to 70 wt% or 10 to 50 wt% of at least one alkyl ketal ester (preferably including at least one highly water miscible species) as described herein, and In many cases, it contains 5 to 70% or 10 to 50% of at least one surfactant.

  Various types of hard surfaces can be cleaned using the hard surface cleaner of the present invention. This hard surface may be, for example, a porcelain or other ceramic material; a metal surface, a wooden surface, a plaster or other drywall surface, a plastic surface, a concrete or cement surface, or other hard surface. This hard surface can be attached to kitchen or bathroom accessories such as sinks, toilets, bathtubs, shower walls; hardwood, tile linoleum, vinyl, cement or other floors; inner walls, windows or mirrors, hard furniture It may be the surface.

  In another aspect, the invention is an aqueous based oily cleaner or oven cleaner. Oily cleaning agents may be useful for industrial, automotive, marine, aerospace, facility, office or home applications.

  The aqueous based oily or oven cleaners of the present invention will most often contain water comprising at least 10% by weight of the total formulation. In some embodiments, water comprises at least 30% by weight of the total formulation, and in further embodiments, up to as much as 80% by weight of the total formulation.

  An important function of this alkyl ketal ester in aqueous-based oil cleaners or oven cleaners is as a solvent for fats or oil stains. Accordingly, aqueous based oil cleaners or oven cleaners may contain at least one water-soluble, slightly lower alkyl ketal ester (such as n-propyl-LGK, n-butyl-LGK, ethyl-LPK and ethyl-LEK). Preferably included, these alkyl ketal esters tend to be more effective oily detergents. This slightly less soluble alkyl ketal ester may be present in an amount of up to 25% by weight and, if present, preferably comprises 0.1 to 10% by weight of the total formulation.

  The aqueous based oily detergent or oven cleaner may comprise an alkyl ketal ester that is highly water miscible, preferably an alkyl ketal ester that is miscible with water in all proportions. This highly water miscible alkyl ketal ester (s) may be present in an amount of 40% or more by weight in the total composition of the aqueous based oily detergent or oven cleaner. In some embodiments, the selected water-miscible alkyl ketal ester may not be miscible with water in all proportions, in such cases, in the composition in an amount below its miscibility limit. It is preferable that it exists in. More preferably, the aqueous oily or oven cleaner according to the present invention comprises at least 1% alkyl ketal ester with high water miscibility and at least 5% by weight with alkyl ketal ester with high water miscibility. The highly water miscible alkyl ketal ester is preferably Me-LGK, MeAcAcGK, Et-AcAcGK or, in particular, Et-LGK, but a mixture of two or more of these can be used.

  Aqueous based oily cleaners or oven cleaners may contain only water and the alkyl ketal ester (s), optionally in combination with perfumes and / or dyes.

Aqueous based oily cleaning or oven cleaning formulations may include the following as a percentage of total formulation weight:
a) Water: 10-80%, more typically 30-80%;
b-1) one or more highly water miscible alkyl ketal ester (s): 0 to 40%, more typically 1 to 40%, more preferably 5 to 25%; , Preferably including at least one of Me-LGK, MeAcAcGK, Et-AcAcGK or Et-LGK;
b-2) One or more water-miscible alkyl ketal ester (s): 0.1-25%, more typically 0.1-10%; the alkyl ketal ester is n- Preferably containing at least one of propyl-LGK, n-butyl-LGK, ethyl-LPK and ethyl-LEK;
c) one or more surfactant (s): 0-25%, preferably 0.1-10%, if present; these surfactants are (1) at least one anionic Or a nonionic surfactant, (2) one or more nonionic surfactants, (3) a mixture of at least one nonionic surfactant and at least one anionic surfactant, ( 4) One or more of C _10-16 alkyl glycosides, alkyl betaines or sulfosuccinates, or (5) (1), (2) or a mixture of (3) and (4) is preferred;
e) One or more organic miscible solvent (s) with slightly lower water miscibility; generally 0-10%, preferably 0.1-5%, if present. This includes, for example, the above alcohols, glycol ethers, hydrocarbons, halogenated hydrocarbons, C _6-9 alkyl aromatic compounds, olefins, terpenes, terpene oxides, terpenoids, oils, May be one or more of natural oil derivatives;
f) One or more highly water miscible organic solvents such as lower alcohols (e.g. ethanol and 1-propanol), acetone: 0-10%, preferably 0.1-5%, if present. In some embodiments, the highly miscible organic solvent (s) can often be removed entirely by the presence of the alkyl ketal ester (s); and
One or more of the above components d) and g) to p) for hard surface cleaners. In some embodiments, components d) -p) may be present in any combination of any two or more thereof. In some embodiments, any or all of components d) -p) may be removed in any particular hard surface cleaning formulation.

  An exemplary oily cleaning / oven cleaning formulation according to the present invention is as follows. The percentages shown are weight percent based on the total formulation weight. In these preparations, the alkyl ketal ester preferably includes one or more types of water-miscible alkyl ketal esters, such as methyl-LPK, ethyl-LPK, ethyl-LEK, n -Propyl-LGK, n-butyl-LGK and the like. For example, one or more highly water miscible alkyl ketal esters such as ethyl-LGK, methyl-LGK, methyl-AcAcGK and ethyl-AcAcGK may also be present. In these formulations, the alkyl ketal ester (s) that are slightly less water miscible functions as an oily detergent and / or a soiling solvent. These alkyl ketal esters have other functions (particularly water-soluble, slightly less water-soluble components; formation of co-solvent mixtures in which one or more other components are dissolved or dispersed, or surface activity Removal or reduction of agents and / or organic solvents or others).

General Formulation 14-Oily detergent containing water for deep and shallow pots Diethylene glycol monobutyl ether 0-10%
Monoethanolamine (MEA) 0.1-1%
1-5% carbonate
Alkyl ketal ester with slightly low water miscibility 1-10%
Alkyl ketal esters with high water miscibility 0-25%, preferably 0.1-25%
Chelating agent (eg, sodium dihydrogen citrate) 1-10%
Anionic surfactant (for example, sodium cumene sulfonate, alkyl ( _C10-16 ) benzenesulfonic acid sodium salt 3 to 29%)
Nonionic surfactant 0-10%
Water (balance of all preparations)

  In the general formulation 14, this slightly less water-miscible alkyl ketal ester functions as an oily detergent and / or soil release agent and may allow for the reduction or removal of diethylene glycol monobutyl ether. Alkyl ketal esters with high water miscibility, when present, can compatibilize water with other components (including slightly less soluble alkyl ketal esters).

  The oily or oven cleaners of the present invention can be applied to any hard surface contaminated with highly hydrophobic materials such as fats, vegetable oils, petroleum products, lubricants, and those types of contaminants and degradation products. Useful for cleaning. These surfaces can be used, for example, in homes, offices and / or industrial equipment, manufacturing and repair facilities (such as automotive repair facilities or other facilities that use petroleum products and / or lubricants).

  Liquid or gel dishwashing formulations are a further embodiment of the invention. These dishwashing formulations may be used for hand washing or machine washing applications. The dishwashing formulations of the present invention most often contain water, which constitutes at least 40% by weight of the total formulation. Water often constitutes at least 50% by weight of the total formulation and may constitute as much as 75% by weight of the total formulation. The liquid or gel dishwashing formulation may comprise a water-miscible alkyl ketal ester, preferably an alkyl ketal ester that is miscible with water in all proportions. The highly water-miscible alkyl ketal ester is preferably Me-LGK, MeAcAcGK, Et-AcAcGK, or, in particular, Et-LGK, but a mixture of two or more of these can be used. Alkyl ketal esters with slightly low water miscibility such as n-propyl-LGK, n-butyl-LGK, ethyl-LPK and ethyl-LEK are used alone or in combination with one or more alkyl ketal esters with high water miscibility. May exist. The alkyl ketal ester (s) may be present in liquid or gel dishwashing formulations in an amount of 25% or more by weight.

  In some embodiments, the alkyl ketal ester (s) present in the liquid or gel dishwashing formulation comprises (a) a solubilizing or emulsifying surfactant or other component and (b) an active cleaning agent. It may perform any or all of several functions such as

In general, liquid or gel dishwashing formulations typically comprise at least one surfactant as described for hard surface cleaning formulations. The surfactant present in the dishwashing preparation for hand washing may be an anionic surfactant or a mixture of one or more anionic surfactants and one or more nonionic surfactants. Many. The surfactant in the machine dishwashing liquid or machine dishwashing gel is more typically a nonionic surfactant to reduce foaming. Alternatively (or additionally), the surfactant may comprise one or more substances derived from plant sources such as one or more C _10-16 alkyl glycosides, alkyl betaines, or sulfosuccinates.

Aqueous or gel dishwashing formulations may include the following as a percentage of the total formulation weight:
a) Water: 40-75%, more typically 50-95%;
b-1) One or more highly water miscible alkyl ketal ester (s): 0-25%, more typically 1-10%; the alkyl ketal ester is Me-LGK, MeAcAcGK, Et -Preferably comprises at least one of AcAcGK or Et-LGK;
b-2) one or more slightly water miscible alkyl ketal ester (s): 0-10%, more typically 0-5%; the alkyl ketal ester is b-1) and b -2) preferably contains at least one of n-propyl-LGK, n-butyl-LGK, ethyl-LPK and ethyl-LEK, provided that at least one of -2) is present;
c) one or more surfactant (s): 0.1 to 45%, preferably 1 to 40%, more preferably 1 to 35%, even more preferably 1 to 10%, optionally Are more preferably 15-35%; these surfactants are: (1) at least one anionic surfactant, (2) at least one nonionic surfactant, (3) at least one mixtures of different non-ionic surfactant and at least one anionic surfactant, (4) C _10-16 alkyl glycoside, one or more of the alkyl betaine or sulfosuccinates, or (5) ( 1), (2) or a mixture of (3) and (4) is preferred;
h) one or more builders or chelating agents, in particular chelating agents such as EDTA or DIDA, 0-30%, preferably 0.1-30% if present, more preferably 1-30 if present 25%, even more preferably 1-10% when present;
i) One or more bleaches including, for example, a chlorine bleach or non-chlorine bleach such as sodium hypochlorite: 0 to 10%, preferably 0.1 to 5%, if present;
o) One or more abrasives, 0-30%, preferably 1-20%, if present.

  Further, the aqueous or gel dishwashing formulation may be any of the components d) to g), j) to n) or p) described above with respect to the hard surface cleaner, alone or any of them. You may include in arbitrary combinations of 2 or more types.

  Some exemplary dishwashing formulations according to the present invention are as follows. The percentages shown are weight percent based on the total formulation weight. In these dishwashing preparations, the alkyl ketal ester preferably includes at least one highly water miscible alkyl ester such as, for example, ethyl-LGK, methyl-LGK, methyl-AcAcGK, and ethyl-AcAcGK. .

  Alkyl ketal esters with slightly low water miscibility, such as methyl-LPK, ethyl-LPK, ethyl-LEK, n-propyl-LGK, n-butyl-LGK, are present especially for the function of degrading oil stains May be. These dishwashing formulations may comprise one or more highly water miscible alkyl ketal esters along with one or more slightly water miscible alkyl ketal esters. As already mentioned, this alkyl ketal ester may perform various functions in these dishwashing formulations in addition to the degradation of oil stains. These include: (1) decomposition and / or removal of soil; (2) compatibility of components, especially water-soluble and slightly less water-soluble components; and (3) one or more other components dissolved or dispersed. One or more of the formation of a co-solvent mixture, (4) removal or reduction of surfactants and / or organic solvents or others.

General Formulation 15-Aqueous detergent for tableware washing machine in gel form, main component (sodium hydroxide) <1.0%
Alkyl ketal ester 0.1-25%, preferably 1-10%
Anionic surfactant (eg, alkylbenzene sulfonate) 0.1- <25%
Thickener (xanthan gum) 1-3%
Abrasive 0-30%
Water (balance of this formulation)

General Formulation 16—Aqueous Liquid Dishwashing Agent for Hand Washing Alkyl Ketal Esters 0.1-25%
Lower alcohol 0-10%
Sodium sulfate 0-15, preferably 0.1-2%
Anionic surfactant (eg, sodium dodecylbenzenesulfonate) 1-30%, preferably 1-20%
Nonionic surfactant 0-25%, preferably 1-15%
Water (balance of this formulation)

General Formulation 17-Mechanical aqueous liquid dishwashing agent II
Alkyl ketal ester 0.1-5%
1-40% nonionic surfactant
Sodium silicate 1-30%
Sodium carbonate 1-25%
Hydrogen peroxide 0-5%
Water (balance of this formulation)

General Formulation 18-Dishwashing microemulsion water 10-40%
1-20% surfactant
Secondary or quaternary _C 4 -C ₅ alcohol 0-50%
Alkyl ketal ester with high water miscibility 0.1-25%
Terpen 0-88%
Alkyl ketal ester with slightly low water miscibility 0.1-50%

  The alkyl ketal esters in the general preparations 15 to 18 can function as oil-based cleaning agents and / or soil release agents, particularly when one of them is a slightly less water-soluble type. This alkyl ketal ester can also compatibilize water with other constituents (including slightly less soluble alkyl ketal esters) and may allow for the reduction or removal of other solvents (alcohols, terpenes, etc.). .

  In other embodiments of the present invention, the cleaning composition is a laundry liquid product and may be for hand or machine cleaning. The laundry liquid formulations of the present invention will most often contain water comprising at least 60% by weight of the total composition. Water often constitutes at least 75% by weight of the total formulation and may constitute as much as 95% by weight of the total formulation. The laundry liquid formulation may comprise an alkyl ketal ester that is highly water miscible, preferably an alkyl ketal ester that is miscible with water in all proportions. The highly water-miscible alkyl ketal ester is preferably Me-LGK, MeAcAcGK, Et-AcAcGK, or, in particular, Et-LGK, but a mixture of two or more of these can be used. This highly miscible alkyl ketal ester (s) may be present in the laundry liquid product in an amount up to 25% by weight. If this highly miscible alkyl ketal ester is not miscible with water in all proportions, it is preferably present in an amount below its miscibility limit. In some embodiments, the laundry liquid product formulation is miscible when present in conjunction with slightly less miscible alkyl ketal esters such as n-propyl-LGK, n-butyl-LGK, ethyl-LPK, and ethyl-LEK. Including one or more of high alkyl ketal esters. The composition preferably comprises at least 1% alkyl ketal ester (s), more preferably at least 5% by weight.

  In laundry liquid products, the alkyl ketal ester (s) can perform any or all of several functions, such as the function of solubilizing and emulsifying surfactants or other ingredients, or the function as an active detergent. You may fulfill.

  Laundry liquid products typically include at least one surfactant as described above for hard surface cleaners. Builders and / or proteolytic enzymes are generally present in laundry liquid products as well as chlorinated and non-chlorinated bleaches.

The laundry liquid formulation may include the following as a percentage of the total formulation weight:
a) Water: 50-95%;
b-1) One or more highly water miscible alkyl ketal ester (s): 0.1-25%, more typically 1-10%; the alkyl ketal ester is Me-LGK, MeAcAcGK , Preferably containing at least one of Et-AcAcGK or Et-LGK;
b-2) One or more slightly water miscible alkyl ketal ester (s): 0-10%, more typically 0-5%; the alkyl ketal ester is n-propyl-LGK, preferably containing at least one of n-butyl-LGK, ethyl-LPK and ethyl-LEK;
c) one or more surfactant (s): 0.1 to 45%, preferably 1 to 40%, more preferably 1 to 35%, even more preferably 1 to 10%, optionally Is more preferably 15-35%; these surfactants are (1) at least one anionic surfactant, (2) a nonionic surfactant, (3) at least one nonionic A mixture of an ionic surfactant and at least one anionic surfactant, (4) one or more of C _10-16 alkylglycosides, alkylbetaines or sulfosuccinates, or (5) (1), ( 2) or a mixture of (3) and (4) is preferred;
h) one or more builders or chelating agents, in particular chelating agents such as EDTA or DIDA: 0-30%, preferably 0.1-30% if present, more preferably 1-30 if present 25%, even more preferably 1-10% when present;
i) One or more bleaches including, for example, a chlorine bleach or non-chlorine bleach such as sodium hypochlorite: 0 to 10%, preferably 0.1 to 5%, if present;
o) one or more abrasives: 0-30%, preferably 1-20%, if present;
p) one or more additives that prevent redeposition, such as, for example, carboxymethylcellulose salt and cellulose acetate polymer, 0-5%, preferably 0.1-2%, if present; and q) (e.g. , Sulfonated triazine-stilbenes, coumarins, imidazolines, diazoles, triazoles, benzoxazolines and biphenylstilbenes) optical brighteners, fluorescent brighteners, and brighteners including fluorescent whiteners, preferably 0.1 to 1%.

  Furthermore, the laundry liquid product may contain any of the components e) to g), j) to n) or p) summarized above alone or in any combination of any two or more thereof. Good. Any or all of components e) -g), j) -n) or p) may be removed from any particular laundry liquid formulation. In particular, it is an advantage of the present invention that the component (s) e) and f) can be removed from the product and their functions are inherited by the alkyl ketal esters present in the formulation.

  Some exemplary laundry liquid formulations according to the present invention are as follows. The percentages shown are weight percent based on the total formulation weight. In these laundry liquid formulations, the alkyl ketal ester may include at least one highly water-miscible alkyl ester such as, for example, ethyl-LGK, methyl-LGK, methyl-AcAcGK, and ethyl-AcAcGK. preferable. These dishwashing preparations may contain one or more highly miscible alkyl esters along with one or more slightly miscible alkyl esters. The function of these alkyl ketal esters in this laundry liquid formulation is the same as described above for the hard surface cleaner.

General Formulation 19-Aqueous liquid detergent for washing Sodium hydroxide 0-1%
About 1% sodium chloride
Nonionic surfactant (e.g. ethoxylated alcohol ( _C12-16 )) 0-20, preferably 0.1-6%
Anionic surfactant (e.g., benzenesulfonic acid, _C10-16 alkyl) 1-20, preferably 1-10%
Builder (s) 0-10
Anti-redeposition agent 0-1%
Proteolytic enzyme 0-2
Brightener (fluorescent agent) 0-1
Buffering agent (s) 0-5
Alkyl ketal ester 0.1-25%
Water (balance of all preparations)

General Formulation 20-Laundry aqueous stain remover Proteolytic enzyme 0- <1%
10-20% surfactant
Chelating agent 0.5-1.5%
Alkyl ketal ester 1-10%
Water (balance of all preparations)

General Formulation 21-Dry Cleaning Aqueous Composition Water 60-95%
Polyacrylate 0.2-0.5%
Mixed glycol ether 0-30%
Alkyl ketal ester 0.1-25%
Surfactant (s)> 0.1%
1,2-octanediol 0.01-5%

  Any of the aforementioned laundry liquid formulations, including the formulations of General Formulations 19-21, reduce the amount of water accordingly and accordingly at least the surfactant concentration, preferably alkyl ketal esters and surfactants Can be prepared in concentrated form by increasing both concentrations. Such concentrated hard surface cleaning formulations may contain up to 50% of a combination of water and / or volatile organic compounds, more typically only 40%. Such concentrated formulations comprise 5 to 70 wt% or 10 to 50 wt% of at least one alkyl ketal ester (preferably including at least one highly water miscible species) as described herein, and In many cases, it contains 5 to 70% or 10 to 50% of at least one surfactant.

In another embodiment of the invention, the cleaning composition is a carpet or other soft surface cleaning product. These products may include the following:
a) Water: 10-90%;
b-1) One or more highly water-miscible alkyl ketal ester (s): 0.1-25%, more typically 1-10%; the alkyl ketal ester is Me-LGK, Me -Preferably comprises at least one of AcAcGK, Et-AcAcGK or Et-LGK;
b-2) One or more slightly miscible alkyl ketal ester (s): 0-25%, more typically 0.1-10% if present: this alkyl ketal ester is n Preferably containing at least one of -propyl-LGK, n-butyl-LGK, ethyl LPK and ethyl-LEK;
c) one or more surfactant (s): 0% to 20%, preferably 0.1-10%, if present; these surfactants are (1) at least one anion A surfactant, (2) a mixture of at least one nonionic surfactant and at least one anionic surfactant, (3) a C _10-16 alkylglycoside, alkylbetaine or sulfosuccinate One or more kinds of (4), (1) or a mixture of (2) and (3) are preferable. These preparations often include at least one builder, which may constitute about 50% by weight of the preparation, and any one or more of the components d) to p) described above. May be included. Any of these components d) to p) may not be present in this product. As before, it is an advantage of the present invention that components e) and f) may be removed from this formulation.

  Some exemplary carpet or soft surface cleaning formulations according to the present invention are as follows. The percentages shown are weight percent based on the total formulation weight. In these formulations, in most cases, the alkyl ketal ester may include at least one highly water miscible alkyl ester such as, for example, ethyl-LGK, methyl-LGK, methyl-AcAcGK and ethyl-AcAcGK. preferable. However, if stronger detergency is required, a slightly less water miscible alkyl ketal ester can be used instead (or in addition). The functions of these alkyl ketal esters in carpet and soft surface formulations are the same as described above for hard surface cleaners.

General Formulation 22-Aqueous detergent for carpet 68-89% water
Builder 1-3%
6-8% anionic surfactant
Glycol ether PnB 0-6%
Alkyl ketal ester 0.1-25%

  In this formulation, the alkyl ketal ester may be able to reduce or eliminate the amount of glycol ether PnB.

General Formulation 23-Carpet Cleaner Detergent Builder 0.1-50%
Alkyl ketal ester with high water miscibility 0.1-25%
Fatty acid alkyl ether / dibasic ester 0-10%
Alkyl ketal ester with slightly low water miscibility 0.1-25%
Surfactant 0.1-10%
Water (balance of all preparations)

General preparation 24- carpet shampoo 58-80% water
6-8% anionic surfactant
Emulsifier / buffering agent 9-12%
Glycol ether PM 0-5%
Alkyl ketal ester with high water miscibility 0.1-25%
2-5% potassium oleate

General Formulation 25-Carpet Shampoo-Medium Foaming Cleaner Water 68-89%
Glycol ether DPM 0-6%
Alkyl ketal ester with high water miscibility 0.1-25%
Builder (trisodium phosphate) 1-3%
Sodium dodecyl sulfate (surfactant) 6-8%

  In this formulation, the alkyl ketal ester may be able to reduce or eliminate the amount of glycol ether DMB.

General Formulation 26-Leather, Vinyl, Plastic Cleaner 77-84% Water
Alkyl ketal ester with high water miscibility 0.1-25%
Ethylene glycol monobutyl ether 0-6%
Propylene glycol monomethyl ether 0-15%
Alkyl ketal ester with slightly low water miscibility 0.1-25%
0-3% isopropanol
Polyethylene glycol 0-17%
Surfactant 0.1-10, preferably 0.1-5
Amyl acetate 0-2%

  In this formulation, the alkyl ketal ester allows for the reduction or removal of isopropanol, amyl acetate and glycol ethers, thereby greatly simplifying the formulation.

  Any of the aforementioned carpet or soft surface cleaners, including the detergents of General Formulations 22-26, are reduced by reducing the amount of water accordingly, at least the surfactant concentration, preferably alkyl. It can be prepared in concentrated form by increasing the concentration of both the ketal ester and the surfactant. Such concentrated carpet or soft surface cleaning formulations may contain up to 60% of a combination of water and / or volatile organic compounds, more typically only 40%. Such concentrated formulations comprise 5 to 70 wt% or 10 to 50 wt% of at least one alkyl ketal ester (preferably including at least one highly water miscible species) as described herein, and In many cases, it contains 5 to 70% or 10 to 50% of at least one surfactant.

  Carpet and soft surface cleaners clean a variety of textile products including carpets, rugs, other fabric floor coverings, curtains, fabric wallpaper, sunshades, upholstery, leather and synthetic leather products, etc. Useful to do.

  In other embodiments, the invention is a powder cleaning product, such as a laundry powder detergent, a powder or granular dishwashing product, a powder bleach cleaner. These products generally include at least one surfactant, an alkyl ketal ester (which may be highly miscible or poorly miscible), and (typically a carrier, an abrasive) in the formulation. (Including one or more of a detergent builder or a solid bleaching component). Powder cleaning products typically contain 1 to 40% surfactant, preferably 5 to 30%, more preferably 10 to 25%. These typically contain 1 to 40%, preferably 5 to 30%, more preferably 10 to 30% builder. These products typically contain less than 5% by weight of water and usually contain only about 2% by weight of water. These cleaning products often also contain chlorinated or non-chlorinated bleach and / or proteolytic enzymes. Other components described for the hard surface cleaner may also be present in harmony with the solid powder form.

  Some exemplary powder cleaning formulations according to the present invention are as follows. The percentages shown are weight percent based on the total formulation weight. In these formulations, in most cases, the alkyl ketal ester includes at least one highly water miscible alkyl ketal ester such as, for example, ethyl-LGK, methyl-LGK, methyl-AcAcGK and ethyl-AcAcGK. It is preferable. However, if stronger detergency is required, a slightly less water miscible alkyl ketal ester can be used instead (or in addition). The function of these alkyl ketal esters in the powder formulation is the same as described above for the hard surface cleaner.

General Formulation 27-Dishwashing powder Alkyl ketal ester 0.1-25%
Nonionic surfactant (s) 4-8%
2-4% chelating agent (eg citric acid)
Sodium carbonate 0.1- <25%
Sodium perborate 0-14%
Pentasodium tripolyphosphate
tripolyphosphate) 0.1- <35%
Proteolytic enzyme 0- <2%
Anionic surfactant (s) 0-10, preferably 2-10%
Sodium silicate> 25%
1-15% anhydrous sodium sulfate
Dye / Pigment / Dye 0-2%
0.1-10% bleach (including sodium hypochlorite)
Potassium hydroxide 0-5%

General Formulation 28-Bleach Powder Cleaner> 60% Calcium Carbonate
Quartz 0.1-1%
Surfactant <25%
Alkyl ketal ester 1-10%
Bleach (organics _Cl 2 _/ O 2) _1~10%

General Formulation 29-Laundry Powder (Cleaning Agent)
Alkyl ketal ester 1-10%
3-7% nonionic surfactant
Alkali metal carbonate 15-40%
Proteolytic enzyme 0.1%
7-13% anionic surfactant
Abrasive (eg, zeolite) 20-40%
Sodium metasilicate 20-40%

  In other embodiments of the invention, the cleaning composition is a disinfectant, a decontamination agent and / or an antistatic agent. Some exemplary cleaning formulations of these types are as follows: The percentages shown are weight percent based on the total formulation weight. In these formulations, in most cases, the alkyl ketal ester includes at least one highly water miscible alkyl ketal ester such as, for example, ethyl-LGK, methyl-LGK, methyl-AcAcGK and ethyl-AcAcGK. It is preferable. However, if stronger detergency is required, a slightly less water miscible alkyl ketal ester can be used instead (or in addition). The function of these alkyl ketal esters in the powder formulation is the same as described above for the hard surface cleaner.

General Formulation 30—Quaternary Amine Aqueous Detergent Ethanol / SD Alcohol 400-5%
Bactericides (eg, dodecyldimethylammonium chloride, alkyl (C _12-16 ) dimethylbenzylammonium chloride) 1-15%
Alkyl ketal ester 1-10%
Nonionic or amphoteric surfactant 0-10%, preferably 0.1-5%
Water (balance of all preparations)

General Formulation 31-Antistatic Dust Spray 1-propoxy-2-propanol 0-4%
Alkyl ketal ester 0.1-25%
Preservative (s) <1%
Cyclodextrin <1%
Water (balance of all preparations)

  The cleaning composition of the present invention may be incorporated on an absorbent material for simple application and / or dosing purposes. The choice of absorbent material may vary widely depending on the intended use. Therefore, for skin cleansing, the cleaning and disinfecting compositions may be incorporated into a cotton pad, fabric pad or sponge. For cleaning surfaces other than the skin, it is advantageous to incorporate the cleaning and bactericidal compositions into sponges, foams or nonwovens. The surface of the sponge may contain an abrasive. Examples of cleaning formulations for application to wipes or sponges are as follows. The percentages shown are weight percent based on the total formulation weight. Alkyl ketal esters for application to wipes or sponges include, for example, at least one highly water miscible alkyl ketal ester such as ethyl-LGK, methyl-LGK, methyl-AcAcGK and ethyl-AcAcGK Is preferred. However, if stronger detergency is required, a slightly less water miscible alkyl ketal ester can be used instead (or in addition). The function of these alkyl ketal esters in the powder formulation is the same as described above for the hard surface cleaner.

General Formulation 32-General Cleaner / Damp Wiped Fiber Composition 2-Butoxyethanol 0-5
Antibacterial agent (for example, alkyl (C _12-16 ) dimethylbenzylammonium chloride) 0.1-0.3
Nonionic or amphoteric surfactant 0-10, preferably 0.1-5
Alkyl ketal ester 0.1-10
Water (formulation balance)

  In this formulation, the alkyl ketal ester may allow 2-butoxyethanol to be reduced or removed from the formulation.

  In another particular embodiment, the cleaning agent of the present invention is a personal care cleaning product for cleaning human skin, hair or other tissues. Examples of these include facial and / or hand cleansers, body cleansers, feminine hygiene products, makeup removers, and various types of shampoos (including baby shampoos, dandruff shampoos, conditioning shampoos, etc.) Is mentioned. Personal care cleaning products according to the present invention can in most cases comprise water comprising at least 20% by weight of the total composition. In some embodiments, water can comprise at least 50% by weight of the total composition and may constitute as much as 99% by weight of the total composition.

Personal care cleansing products typically include one or more emollients that are substances that soften the skin. These emollients include substances in one or more of the following classifications s) -w):
s) paraffin oil, naphthenic oil or aromatic mineral oil;
t) a melting point of less than 45 ° C., a molecular weight of at least 190, comprising at least one amide or ester group and at least one alkyl chain comprising at least 8 carbon atoms, 1 to 99% water Nonionic organic compound having a water solubility of about%. These include a range of natural oils and products of synthetic esters and amides, which have little or no surfactant properties (HLB less than 4, preferably less than 2). In many cases, it functions as an emollient in personal care cleaning products.

Examples of substances include:
t) vegetable oils and animal fats and derivatives _thereof, alkyl esters of _{C 8-24} straight or branched chain _{C --24} fatty, _{C 8-24} diesters of dicarboxylic _{acids, C 8-24} C _8-24 fatty acid esters of linear or branched alkanoic acids, C _8-24 , in particular, C _12-15 alkyl benzoates, poly (propylene oxide) esters of C _8-24 fatty acids, aromatic two C _8-24 linear or branched dialkyl esters of acids, C _8-24 difatty acid esters of aromatic _diacids , etc .; C _8-24 linear or branched alkyls of C _8-24 fatty acids amides, _{C 8-24} diamides of dicarboxylic _{acids, C 8-24 C 8-24} fatty acid amides of alkanoic acids linear or _{branched, C 8-24} fatty acid poly (propylene oxide) Ami S, dialkylamides of C _8-24 straight or branched chain aromatic diacids, C _8-24 di fatty acid amides of aromatic diacids and the like;
u) A nonionic organic silicone compound having a melting point of less than 45 ° C. and having a water solubility of about 1% with respect to 99% of water. Examples include dimethicone and cyclopentasiloxane;
v) Long chain (8 or more carbon atoms) alcohols such as 1-octanol, 1-decanol, 1-docecanol, cetyl alcohol. These alcohols can serve a variety of functions, including thickening and solubilizing / compatibilizing functions, and can also function as emollients;
w) Waxes. Waxes include ceresin wax, montan wax, ozokerite wax, peat wax, paraffin wax, microcrystalline wax, polypropylene wax and other polymerized poly α-olefin wax, substituted amide wax, petrolatum wax, esterification or saponification. Waxes and the like as well as waxes obtained from plants or animals are included.

  When present in the agglomerates, the components s) to w) constitute 0.5 to 50% by weight of the personal care cleaning product. Substances o) to s) tend to be highly hydrophobic and therefore products and water containing these substances tend to exist in the form of emulsions.

  The personal care cleansing product may include one or more surfactants, particularly for multipurpose skin cleansers and shampoo products. The makeup remover according to the present invention may not include a surfactant in some embodiments.

  Any of the surfactants described above can be present in personal care cleaning products including various sulfuric and sulfonic acid surfactants, sulfosuccinic acid surfactants, betaine derivatives, and the like. Personal care cleaning products typically include at least one “first” surfactant that facilitates foaming and cleaning, such as isothiocyanate, sulfuric acid and sulfonic acid surfactants. "Secondary" or "enhancing foam" surfactants such as betaine, sarcosinate, sulfosuccinate, taurate, ether sulfate, glucoside, amine oxide, sultain, lactylate, and / or glutamate surfactants are , Often in combination with a “first surfactant”.

  If present, this surfactant (s) may constitute 0.5-30% of the total weight of the personal care cleaning product.

  The personal care cleaning product of the present invention includes at least one alkyl ketal ester of structure I. In some embodiments, at least one highly water miscible alkyl ketal ester, preferably an alkyl ketal ester that is miscible with water in all proportions, is present in the personal care cleaning product. Examples of such highly water-miscible alkyl ketal esters include Me-LGK, MeAcAcGK, Et-AcAcGK or, in particular, Et-LGK, but a mixture of two or more alkyl ketal esters can be used. . In some embodiments, the highly water miscible alkyl ketal ester is a slightly less water miscible alkyl ketal ester such as, for example, n-propyl-LGK, n-butyl-LGK, ethyl-LPK, and ethyl-LEK. May be present together. In yet another embodiment, the alkyl ketal ester with slightly less water miscibility is used by itself, ie, in the absence of the alkyl ketal ester with high water miscibility. The amount of alkyl ketal ester present in the personal care cleaning product is about 1 to about 50% by weight of the total composition, preferably about 1 to about 20% by weight of the total composition, more preferably the total composition. It can be about 3 to about 15% by weight, or about 2 to about 10% by weight of the total composition.

  The function of the alkyl ketal ester in a personal care cleaning product may be as an emulsifier and / or a co-solvent that increases the stability of the product and / or solubilizes one or more substances into another. Good. Alkyl ketal esters with high water miscibility perform particularly well this emulsifying and / or cosolvent function. Alkyl ketal esters with slightly low water miscibility can perform cosolvent functions and viscosity reducing functions, and are often all effective detergents. A personal care cleansing product containing at least 1% by weight of a slightly less soluble alkyl ketal ester is a very effective makeup remover.

  The above components d) to w) may be present in the personal care cleaning product of the present invention. Any two or more of them can be present together. Any or all mixtures of components d) -w) may be removed from any particular personal care cleaning product formulation. Component d) is typically present in the spray formulation. In some cases, a single substance may serve multiple functions in a personal care cleaning product.

  In addition, personal care cleaning products include various polyquat compounds and one or more hair conditioners such as silicone compounds (such as silicone copolyols and silicones containing amino groups); such as glycol stearate or glycol distearate. One or more opacifiers; one or more specific functional activities such as anti-dandruff, acne prevention, skin whitening, vitamins, aloe, antioxidants, UV absorbers and other active agents; one or more Thickeners or suspending agents may be included.

  Some exemplary personal care cleaning products according to the present invention are as follows. The percentages shown are weight percent based on the total formulation weight.

General Formulation 33-Mild Skin Cleanser Part A:
Warm distilled water 40-75%
Part B:
Sulfosuccinate 4-30%
Cocobetaine 4-30%
Palm oil fatty acid PEG-7 glyceryl 1-10%
Distearic acid PEG-150 0.5-5%
Part C: 0.1 to 2% phenoxyethanol
Alkyl ketal ester with high water miscibility 0.1-20%
Alkyl ketal ester with slightly low water miscibility 0-10%

General Formulation 34-Aloe Vera Facial Lotion Part A:
45-75% warm distilled water
Part B:
Sulfosuccinate 4-30%
Cocobetaine 4-30%
Glycol stearate IP 2-6%
Part C:
Aloe Vera 10 x Concentrate 0.1-5%
Phenoxyethanol / SA 0.1-2%
Alkyl ketal ester with high water miscibility 0.1-20%
Alkyl ketal ester with slightly low water miscibility 0-10%

  This alkyl ketal ester (s) can be added to any of parts A, B and C of general formulation 33 or 34. This highly water miscible alkyl ketal ester functions as a co-solvent with water and can solubilize or compatibilize other components (particularly the substance of Part B and phenoxyethanol). In some cases, the presence of a highly water-miscible alkyl ketal ester can increase the concentration of the moiety B material and phenoxyethanol and form a higher concentration product.

General Formulation 35-Shampoo Part A:
20-50% ammonium lauryl sulfate or sodium salt
Laureth ammonium sulfate or sodium salt 15-30%
Lauroyl sarcosine sodium 2-10%
Cocamidopropylamine oxide 2-10%
PPG ester or PEG ester 0.1-3%
Polyquat aqueous solution 1-3%
Ethylene glycol distearic acid 1-3%
Part B:
Plant extract / derivative solution and carrier 0-1%
Hydrolyzed silk solution and carrier 0.05-0.2%
Hydrolyzed keratin protein or silk protein 0-2%
Methyl isothiazolinone 0-0.2%
Part C:
Cocamidopropyl hydroxysultain 5-15%
Cocamidopropyl betaine 3-10%
Alkyl ketal ester with high water miscibility 0.1-20%
Alkyl ketal ester with slightly low water miscibility 0-10%

General Formulation 36-Baby Shampoo Part A:
10-20% ethoxylated glycerides
Ethoxylated thickener 0-2%
Part B:
Laureth sulfate sodium salt 10-30%
Cocamidopropyl hydroxysultain 8-15%
40-75% deionized water
Part C:
Propylene glycol and diazolidinyl urea and methyl paraben and paraben 0.1-2%
HCl, 10% solution, appropriate amount 0.1 to 20% alkyl ketal ester with high water miscibility
Alkyl ketal ester with slightly low water miscibility 0-10%

  This alkyl ketal ester (s) can be added to any of all of parts A, B and C of general formulation 35 or 36. This highly water miscible alkyl ketal ester functions as a co-solvent with water and can solubilize or compatibilize other components (particularly the substance of Part B and phenoxyethanol). In some cases, the presence of a highly water-miscible alkyl ketal ester can increase the concentration of the substance in Part B and make a more concentrated shampoo product.

  Any of the above formulations 1 to 36 may contain a beautifying agent such as a dye and / or fragrance.

  The cleaning product according to the invention can be used in any convenient way. Cleaning is generally accomplished by contacting the cleaning product with a soil substrate, and then removing the cleaning product along with the soil removed. In particular, if the cleaning product is in a concentrated form, it may be diluted with water or other solvent prior to applying the cleaning product. Removal can be accomplished by one or more steps of, for example, wiping, vacuuming, mechanical removal (eg, with a cloth, mop broom or sponge), absorption into absorbent material, and / or rinsing. Can do. To further loosen the soil from the substrate, if necessary, mechanical soil removal steps such as spraying, rubbing, brushing and / or scrubbing can be performed.

  Since numerous improvements and modifications within the scope of the invention will be apparent to those skilled in the art, the invention will be described in further detail in the following examples, which are meant to be illustrative only. Unless otherwise stated, all parts, all proportions, and all ratios reported in the following examples are by weight and all reagents used in these examples are from the chemical manufacturers listed below. Obtained or available, or may be synthesized by conventional techniques. In the following examples, ethyl-LGK or Et-LGK corresponds to an alkyl ketal ester formed from ethyl levulinate and glycerin. Ethyl-LPK or Et-LPK represents an alkyl ketal ester formed from ethyl levulinate and 1,2-propylene glycol.

Example 1-Bleach Stability Evaluation Using Et-LPK The purity of an Et-LPK sample was determined by GC-FID (Model No. 7890A gas chromatograph w / flame ionization detector; Agilent Technologies, Santa Clara, CA). Measure with In a 20 ml vial (borosilicate scintillation; VWR International, Westchester, PA), mix 2 ml of 6% sodium hypochlorite in water (bleach; Clorox, Oakland, CA) with 8 ml of Et-LPK. To form a mixture. This mixture is stirred vigorously to produce an almost clear solution. The mixture is further stirred overnight on a magnetic stir plate with a magnetic stir bar. Upon standing, the mixture separates into two phases (an organic phase above and an aqueous phase below). The sample of the organic phase is analyzed by GC-FID, and after mixing, the purity of Et-LPK is examined. The GC-FID results showed that there was almost no change in the purity of Et-LPK when compared to the purity of the original Et-LPK. This indicates that Et-LPK is stable in concentrated solutions of sodium hypochlorite often found in consumer bleach products.

Examples 2-3 Stability Evaluation of Bleach and Peroxide with Et-LGK The ingredients shown in Table 1 were mixed in a 20 ml borosilicate glass scintillation vial followed by vigorous stirring and clear colorless Examples 2-3 and control (non-bleaching) formulations are prepared by forming a solution of After standing at room temperature for 3 days, all formulations are clear, colorless and uniform solutions.

  After 96 hours storage, GC / FID analysis is performed to evaluate the stability of Examples 2 and 3 and Comparative Sample A. Three analyzes are performed with each test sample. For the control, it can be seen that the concentration of Et-LGK is about 10%. For Example 1, an Et-LGK concentration of about 9.4% indicates that this material was slightly degraded in the presence of chlorinated bleach. For Example 2, the same Et-LGK concentration as the control indicates no interaction with the hydrogen peroxide bleach.

Example 4-Solubilization of Et-LPK In a 20 ml scintillation vial, several mixtures of the three components Et-LGK, water and Et-LPK were mixed by shaking the above material at room temperature. To prepare. The prepared mixture is visually analyzed for miscibility. In this test, a clear mixture is considered miscible, and a mixture that is turbid or forms two or more different phases is considered immiscible. The results for various mixtures are listed in Table 2.

  As shown in Table 2, Et-LPK is immiscible in water at the 10.9% level. A mixture of water and Et-LGK is a much better solvent for Et-LPK than water alone. As shown in Mixture 18, an Et-LPK concentration of approximately 55 wt% can be obtained in the miscible mixture.

Example 5 and Comparative Samples AC Solubilization of Isobutyl Isobutyrate (IBIB) A mixture of water and isobutyl isobutyrate (IBIB; Acros Organics, Thermo Fisher Scientific Division, Waltham, Mass.) Prepare in volume ratios of 10/90, 25/75, 50/50, 75/25 and 90/10. All mixtures form immiscible mixtures. To assess the ability of Et-LGK to solubilize IBIB in water, each of these mixtures was mixed with vigorous stirring in a 20 ml scintillation vial at about 25 ° C. until a clear solution was obtained. Add In each case, the concentration (volume%) of Et-LGK required to form a clear solution is summarized in Table 3.

  In comparison, propylene glycol methyl ether (Acros Organic, Thermo Fisher Scientific, Waltham, Mass.), Ethylene glycol monobutyl ether (Sigma Aldrich; St. Louis, MO) and dipropylene glycol methyl ether (Sigma Aldrich); St. Louis, MO) evaluates the ability to form a clear solution containing water and IBIB in the same way. In each case, the concentrations (% by volume) of these comparative solvents required to form a clear solution are summarized in Table 3 as comparative samples A, B, and C, respectively.

＊は本発明の実施例ではない。比は体積比である。ＰＧＭＭＥは、プロピレングリコールモノメチルエーテルである。ＥＧＭＢＥは、エチレングリコールモノブチルエーテルである。ＤＰＧＭＭＥは、ジプロピレングリコールモノメチルエーテルである。

* Is not an example of the present invention. The ratio is a volume ratio. PGMME is propylene glycol monomethyl ether. EGMBE is ethylene glycol monobutyl ether. DPGMME is dipropylene glycol monomethyl ether.

  Et-LGK shows that it has the ability to compatibilize water and IBIB, similar to the ability of each of the comparative cosolvents.

Example 6 and Comparative Samples D-F-Solubilization of Castor Oil A mixture of water and castor oil (Chemistry Store.com; Cayce, SC) was mixed 10/90, 25/75, 50/50. , 75/25 and 90/10 volume ratios. All mixtures form immiscible mixtures. In order to assess the ability of Et-LGK to solubilize castor oil in water, each of these mixtures was stirred with vigorous stirring in a 20 ml scintillation vial at about 25 ° C. until a clear solution was obtained. Add LGK. In each case, the concentration (vol%) of Et-LGK required to form a clear solution is summarized in Table 4.

  In comparison, propylene glycol methyl ether (Acros Organic, Thermo Fisher Scientific, Waltham, Mass.), Ethylene glycol monobutyl ether (Sigma Aldrich; St. Louis, MO) and dipropylene glycol methyl ether (Sigma Aldrich); St. Louis, Missouri) evaluates the ability to form clear solutions containing water and castor oil in the same manner. In each case, the concentrations (volume%) of these comparative solvents required to form a clear solution are summarized in Table 4 as comparative samples D, E, and F, respectively.

＊は本発明の実施例ではない。比は体積比である。ＰＧＭＭＥは、プロピレングリコールモノメチルエーテルである。ＥＧＭＢＥは、エチレングリコールモノブチルエーテルである。ＤＰＧＭＭＥは、ジプロピレングリコールモノメチルエーテルである。

* Is not an example of the present invention. The ratio is a volume ratio. PGMME is propylene glycol monomethyl ether. EGMBE is ethylene glycol monobutyl ether. DPGMME is dipropylene glycol monomethyl ether.

  Et-LGK shows that it has the ability to compatibilize water and castor oil, similar to the ability of each of the comparative cosolvents.

Example 7 and Comparative Examples GI Solubilization of Soybean Methyl Ester A mixture of water and soy methyl ester (Stepan Chemical Co .; Northfield, Illinois) was mixed with 10/90, 25/75, 50 / Prepare in volume ratios of 50, 75/25 and 90/10. All mixtures form immiscible mixtures. To evaluate the ability of Et-LGK to solubilize soy methyl ester in water, in each of these mixtures with vigorous stirring in a 20 ml scintillation vial at about 25 ° C. until a clear solution was obtained. -Add LGK. Table 5 summarizes the concentration (% by volume) of Et-LGK required to form a clear solution in each case.

  In comparison, propylene glycol methyl ether (Acros Organic, Thermo Fisher Scientific, Waltham, Mass.), Ethylene glycol monobutyl ether (Sigma Aldrich; St. Louis, MO) and dipropylene glycol methyl ether (Sigma Aldrich); St. Louis, MO) evaluates the ability to form clear solutions containing water and soy methyl ester in the same manner. In each case, the concentrations (% by volume) of these comparative solvents required to form a clear solution are summarized in Table 5 as comparative samples G, H, and I, respectively.

＊は本発明の実施例ではない。比は体積比である。ＰＧＭＭＥは、プロピレングリコールモノメチルエーテルである。ＥＧＭＢＥは、エチレングリコールモノブチルエーテルである。ＤＰＧＭＭＥは、ジプロピレングリコールモノメチルエーテルである。

* Is not an example of the present invention. The ratio is a volume ratio. PGMME is propylene glycol monomethyl ether. EGMBE is ethylene glycol monobutyl ether. DPGMME is dipropylene glycol monomethyl ether.

  As can be seen from the data in Table 5, Et-LGK and all of the comparative cosolvents are compatible with water and soy methyl ester oil.

Example 8 and Comparative Examples J to L-2,2,4-Trimethyl-1,3-pentanediol (2-methylpropanoic acid) solubilized water and 2,2,4-trimethyl-1,3-pentanediol Mixtures of (2-methylpropanoic acid) ("Texanol") (Sigma Aldrich; St. Louis, MO) were prepared in volume ratios of 10/90, 25/75, 50/50, 75/25 and 90/10 To do. All mixtures form immiscible mixtures. To assess the ability of Et-LGK to solubilize texanol in water, each of these mixtures was mixed with vigorous stirring in a 20 ml scintillation vial at about 25 ° C. until a clear solution was obtained. Add Table 6 summarizes the concentration (% by volume) of Et-LGK required to form a clear solution in each case.

  In comparison, propylene glycol methyl ether (Acros Organic, Thermo Fisher Scientific, Waltham, Mass.), Ethylene glycol monobutyl ether (Sigma Aldrich; St. Louis, MO) and dipropylene glycol methyl ether (Sigma Aldrich); St. Louis, Missouri) evaluates the ability to form clear solutions containing water and texanol in the same manner. In each case, the concentrations (% by volume) of these comparative solvents required to form a clear solution are summarized in Table 6 as comparative samples G, H, and I, respectively.

＊は本発明の実施例ではない。比は体積比である。ＰＧＭＭＥは、プロピレングリコールモノメチルエーテルである。ＥＧＭＢＥは、エチレングリコールモノブチルエーテルである。ＤＰＧＭＭＥは、ジプロピレングリコールモノメチルエーテルである。

* Is not an example of the present invention. The ratio is a volume ratio. PGMME is propylene glycol monomethyl ether. EGMBE is ethylene glycol monobutyl ether. DPGMME is dipropylene glycol monomethyl ether.

As can be seen from the data in Table 6, Et-LGK and all of the comparative cosolvents can compatibilize water and texanol.

Examples 9 and 9A and Et-LGK and Et-LPK in comparative sample M-cleaning formulations
Cleaning formulations 9 and 9A are prepared by mixing the following components in a 20 ml scintillation vial: 4% solvent (Example 9-Et-LGK and Example 9A-Et-LPK); 4.5 % Nonionic surfactant (Biosoft N91-6, Stepan; Northfield, Ill.); 0.5% sodium citrate dihydrate (Fisher Scientific, Thermo Fisher Scientific Division, Waltham, Massachusetts), and the balance of the formulation being water. Comparative sample M is prepared by replacing the solvent described in Examples 9 and 9A with additional water. Examples 9 and 9A and comparative sample M are heated separately with vigorous stirring and visually observed to record the temperature at which these formulations become cloudy. The cleaning formulation of Example 9 becomes cloudy at about 48 ° C. The results obtained in Example 9 are similar to those obtained when replacing Et-LGK with propylene glycol monomethyl ether, ethanol and ethylene glycol n-butyl ether on a weight basis. The turbidity of Example 9A at a temperature slightly above room temperature is consistent with the low water solubility of Et-LPK.

Vegetable oil-based soil composition (0.5-1.0 g) according to CPA DCC-17 “Oil Soil Test Method for Evaluating Spray and Wipe Cleaning Agents Used on Hard and Matte Surfaces” To prepare. The soil composition is applied to 5 inch x 7 inch (12.5 cm x 15.5 cm) white porcelain on a stainless steel tile. The soiled tiles were placed vertically in an oven at 150 ° C. for 2 hours and allowed to change overnight at room temperature. Sponge (ASTM
The cleaning test is carried out using a Gardner Linear Washability Tester (Byk-Gardner USA; Columbia, MD) present on the adhesive surface of D 2486). Examples 9, 9A and comparative sample M are evaluated separately. The tiles are washed for 25 cycles or until> 98% of these tiles are clean (until either happens first).

  The soiled tile exposed to Example 9A is determined to clean in as little as 12 cycles. The soiled tile exposed to Example 9 shows that 85% soil is removed in 25 cycles, while Comparative Sample M removes only 80% of soil after 25 cycles.

Examples 10-15-Detergent Stability Evaluation Detergent Examples 10-12 are prepared by mixing the following components: 4% Et-LGK; 4.5% nonionic surfactant (Biosoft N91-6, Stepan, Northfield, Ill.); 0.5% anionic surfactant, 0.5% sodium citrate dihydrate (Fisher Scientific, Thermo Fisher Scientific) Department; Waltham, Massachusetts), and water (formulation balance). In Example 10, the anionic surfactant is dodecylbenzene sulfonic acid (Acros Organics; Waltham, Mass.); In Example 11, the anionic surfactant is BioTarget PAS-8S (Stepan, North In Example 12, the surfactant is Dowfax ClO-1 (Dow Chemical Co., Midland, Michigan). The cleaning formulations of Examples 10-12 are heated separately with vigorous stirring and visually observed to determine the temperature at which these solutions become cloudy. Formulations 10-12 become cloudy at 72 ° C, 55 ° C and 60 ° C, respectively. Similar results are observed when Et-LGK is replaced on a weight basis with dipropylene glycol monomethyl ether or ethylene glycol monobutyl ether.

  Examples 13-15 were described with respect to Examples 10-12 above, except that in all cases the nonionic surfactant was Biosoft N25-7 (Stepan, Northfield, IL). Prepare and test in the usual way. When the cleaning formulations of Examples 13-15 are visually observed, they become cloudy at 80 ° C, 54 ° C and 67 ° C, respectively. In Examples 13-15, replacing dipropylene glycol monomethyl ether or ethylene glycol monobutyl ether with Et-LGK on a weight basis would give the same or lower turbidity, which would allow nonionic surfactants. From the point of view of solubilization, we show that Et-LGK performs the same or better function in these formulations than these conventional solvents.

Examples 16 to 17 and Comparative Examples N and O-Soft Surface Cleansing Formulation (Pre-Spotter for Laundry)
Examples 16 and 17 are prepared by mixing the following components shown in Table 7.

  In a separate 3 "x 4" (7.5 cm x 10 cm) cotton / polyester sample (Scientific Service S / D; Sparrow Bush, NY), the following spots (Scientific Service S / D; Sparrow Bush, all stains from New York State) pre-applied: ballpoint pen ink (product number 7435WRL, lot number 1345), used lubricant (product number 7435WRL, lot number 1912), lipstick (product number 7435WRL) , Lot number 1351), red wine (product number 7435WRL, lot number 1612), coffee (product number 7435WRL, lot number 1910) and blood (product number PEDP7435WRL, lot number 1457). Two samples of each sample are treated with 2 ml of either Example 16 or Example 17, followed by washing in a commercial washing machine after 2-4 hours. The washing step is performed in a warm / cold setting and dried in a durable press setting using three white cotton towels for stabilization. Three samples are analyzed for each test. The cleaned and dried swatches are examined by five panelists at a time and ranked for cleanliness based on a 1-5 scale (1 being the lowest, 5 being the best). The performance test of a laundry press potter is based on CSPA DCC-Il ("Home Prewash Spotter Stain Remover"). Comparative Example N is performed as in Examples 16-17, except that a commercially available pre-spotting formulation (Shout ™; SC Johnson; Racine, Wisconsin) was used. Comparative Example O is the result of a similar washing process that does not include the prespotting formulation. The results are shown in Table 8.

  Example 16 outperforms Comparative Samples N and O for ink and lipstick stains, and Example 17 outperforms for red wine and coffee stains. However, Comparative Sample N contains proteolytic enzymes that are not present in Examples 16-17 or Comparative Sample O.

Examples 18 and 19 and Comparative Samples P and Q: Laundry Concentrated Cleaning Formulations Examples 18 and 19 and Comparative Samples P and Q were mixed with the components listed in Table 9 in a 20 ml borosilicate glass scintillation vial. Prepare by shaking by hand. In each of Examples 18 and 19, Et-LGK is replaced with a portion of water. All four formulations are clear and homogeneous solutions at room temperature.

  Viscosities of Examples 18 and 19 and Comparative Samples P and Q are measured at 25 ° C. using a Brookfield DV-II + Pro viscometer with 518 spindles. The results are summarized in the cP column of Table 10.

  As can be seen from the data in Table 10, the presence of Et-LGK significantly reduces the viscosity of the formulation.

  Examples 18-19 and comparative samples P and Q are placed in a 2 ° C. refrigerator for 1 hour. Comparative sample Q becomes turbid after 1 hour and all other solutions remain clear. After heating again in a 50 ° C. oven, the entire solution is clear and uniform.

  Examples 18-19 and comparative samples P and Q are placed in a −16 ° C. freezer for 1 hour to freeze the entire solution. Thereafter, all of the formulation is allowed to thaw at room temperature. After thawing, comparative sample Q remains cloudy. All remaining formulations are clear and return to a homogeneous solution. Thereafter, Examples 18 and 19 and Comparative Sample P remain clear even after freezing-thawing for two or more cycles in the same manner. These results indicate that adding Et-LGK to a laundry concentrate cleaning formulation provides a temperature-stable laundry cleaner.

Examples 20-21-Concentrated cleaning formulations for cold water laundry Examples 20-21 are prepared in the same manner as described in US Patent Publication No. 2010/0041577 (Metalucca). The formulations are summarized in Table 11. The combined components are mixed in a 20 ml borosilicate glass scintillation vial, heated to 50 ° C. for 15 minutes and stirred mechanically at room temperature overnight. Both formulations are clear and uniform solutions. The viscosity of the above formulation is measured using a Brookfield DV-II + Pro viscometer with 518 spindles. The results are shown in Table 11.

  The viscosity of these solutions is significantly lower than that of solutions prepared without the alkyl ketal ester.

  Examples 20 and 21 remain homogeneous after being placed in a 2 ° C. refrigerator overnight, and remain uniform after 3 freeze-thaw cycles as described for Examples 18 and 19.

Example 22 and Comparative Sample R-Aqueous Cleaning Formulation for Deep Pot and Shallow Pot Example 22 and Comparative Sample R were mixed in a 20 ml borosilicate glass scintillation vial with the ingredients listed in Table 12 and shaken by hand. Prepare by. Both formulations are clear and uniform solutions.

  Each of Example 22 and Comparative Sample R is heated to 60 ° C. on a hot plate. Both formulations remain clear and homogeneous solutions at 60 ° C., indicating that both formulations have turbidity points above 60 ° C. Both solutions remain uniform after cooling in a 2 ° C. refrigerator for 1 hour. These results show that alkyl ketal esters can be replaced with diethylene glycol butyl ether in oily cleaning formulations.

Example 23-Aqueous Gel Formulation for Tableware Example 23 is prepared from the ingredients shown in Table 13.

  NaOH is added to the water in a 2 ounce polypropylene container and heated to 50 in an oven for 1 hour. The heated solution is stirred on a heated stir plate and xanthan gum is added over 2-3 minutes. Surfactant and Et-LGK are added sequentially to this stirred solution. Heat is turned off and potassium carbonate is added to this solution with stirring for 5 minutes at room temperature. Remove vial from stir plate. The appearance of this product is translucent gray. This product is viscous but can be poured. After stirring for 5 days at room temperature, the product thickens to a white gel that does not refract when turned over on one side.

  When Example 23 is repeated replacing Et-LGK and water, the product is very viscous and cannot be poured. However, after 5 days, when turned over on one side, it forms a thin gel that cannot retain its shape. Therefore, Et-LGK is harder and produces an excellent gel product.

Examples 24-26-Baby Shampoo Formulations Shampoo formulations 24-26 are prepared from the ingredients summarized in Table 14.

  All of these formulations are clear and uniform.

Examples 27-29-Glossy Mild Shampoo Examples 27-29 are prepared from the ingredients shown in Table 15.

全ての製剤の色は白色で、均一である。

All formulations are white in color and uniform.

Examples 30-31-Curly Hair Shampoo Formulation Examples 30-31 are prepared from the ingredients shown in Table 16.

実施例３０および３１は、予想通り、不透明で、均一である。

Examples 30 and 31 are opaque and uniform as expected.

Examples 32-33-Body Wash Formulations Containing Green Tea Examples 32-33 are prepared from the ingredients shown in Table 17.

Examples 34-35-Shampoo Formulation Examples 34-35 are prepared from the ingredients shown in Table 18.

  Examples 34-35 are both transparent and uniform.

Examples 36-37-Body Wash Formulation for Showers Examples 36-37 are prepared from the ingredients shown in Table 19.

Examples 38-39-Hard Surface Cleaners Prepare Phase I and Phase II in separate 20 ml borosilicate glass scintillation vials, then slowly pour Phase II into Phase I with stirring to The preparation of These components are summarized in Table 20.

  Example 38 is a clear, less viscous solution, while Example 39 is a cloudy, slightly viscous emulsion that remains stable at room temperature overnight.

Examples 40 and 41-Hard Surface Wash Concentrate By preparing Phase I and Phase II in separate 20 ml borosilicate glass scintillation vials and then slowly pouring Phase II into Phase I with stirring. The following formulation is made. These ingredients are summarized in Table 21.

  Examples 40 and 41 are both clear and low viscosity solutions. When diluted with 8.5 wt% water, Example 40 remains clear, while Example 41 is cloudy and slightly viscous.

Example 42-Soap residue remover Mix 5 wt% tetrasodium EDTA, 10 wt% anionic surfactant (Biosoft D-40), 5 wt% Et-LGK and 80 wt% water. Thus, Example 42 is produced. A clear and uniform solution is obtained.

Example 43-Makeup Remover Formulation Without Surfactant Example 43 is made by mixing 5 wt% Et-LPK, 19.5 wt% Et-LGK and 5 wt% water. The product is a clear, uniform makeup remover formulation without surfactant.
Examples 44-48-Eye Makeup Remover Formulation Containing Surfactants Examples 44-48 are prepared from the ingredients summarized in Table 22. Add the ingredients of Examples 44-48 to the beaker in the order summarized in Table 23 and mix thoroughly.

＊本発明の実施例ではない。

* This is not an example of the present invention.

  Each of Examples 44-48 is a clear, uniform solution.

Claims (14)

A solution containing a solute dissolved in an aqueous co-solvent mixture, the aqueous co-solvent, even without water and small is a mixture containing one alkyl ketal ester le, the alkyl ketal ester has the formula (II)

Or formula (III)

Or formula (IV)

Or formula (V)

( Wherein R ⁵ is methyl, ethyl, n-propyl or n-butyl )
A cleaning product comprising a solution having the structure: The solute comprises at least one organic compound having a 1 wt% or less of a water-soluble to water 99 wt%, the cleaning product according to claim 1. The solute has a water solubility of less than 20% by weight with respect to 80% by weight of water, and includes (1) an alkyl ketal ester, (2) a surfactant, and (3) a maximum of 30 carbon atoms. A chain, branched or cyclic aliphatic hydrocarbon, (4) an α-olefin having 2 to 20 carbon atoms and a boiling point of at least 100 ° C., (5) an aromatic compound, (6 ) Monoalkyl benzene or polyalkyl benzene each alkyl group containing 1 to 12 carbon atoms, (7) alkane chloride, (8) alkane bromide, (9) terpene, (10) melting point less than 45 ° C., molecular weight There is at least 190, at least one amide group or ester group, and includes one of the alkyl chain even without including less at least 8 carbon atoms and 1 wt% or less with respect to 99% by weight of water A nonionic organic compound having a water-soluble, less than 1% by weight of a water-soluble (11) glycol ether, (12) glycol ether acetates, (13) is less than the melting point 45 ° C., and relative to 99% by weight of water A cleaning product according to claim 1 or 2, selected from one or more of a nonionic organosilicone compound, (14) a long chain alcohol containing at least 8 carbon atoms, or (15) a wax. The cleaning according to any of claims 1 to 3, wherein the aqueous co-solvent mixture further comprises a solvent (s) having a molecular weight of 250 or less and a water solubility of 20 wt% or more with respect to 80 wt% of water. Product . The cleaning product according to any one of claims 1 to 4, wherein the solute is present at a concentration higher than the solubility limit of the solute in water. An emulsion comprising at least one continuous phase comprising water and an alkyl ketal ester, wherein the alkyl ketal ester is represented by formula (II)

Or formula (III)

Or formula (IV)

Or formula (V)

( Wherein R ⁵ is methyl, ethyl, n-propyl or n-butyl )
A cleaning product comprising an emulsion having the structure: The cleaning product according to any one of claims 1 to 6 , which is a hard surface cleaning agent, an oven cleaning agent, an oily cleaning agent, a dish cleaning product, a laundry liquid product, or a soft surface cleaning agent. The cleaning product according to any one of claims 1 to 6 , which is a personal care cleaning product. The cleaning product according to any of claims 1 to 5, further comprising at least one hair conditioner, which is a personal care cleaning product. The cleaning product of claim 6, further comprising at least one hair conditioner present in the dispersed phase and being a personal care cleaning product. a) 20-99% by weight of water;
b) 0.1-25% by weight of at least one alkyl ketal ester (s); and c) 0.1-20% by weight of at least one surfactant.
A cleaning formulation comprising
The alkyl ketal ester is represented by the formula (II)

Or formula (III)

Or formula (IV)

Or formula (V)

( Wherein R ⁵ is methyl, ethyl, n-propyl or n-butyl )
A cleaning preparation having the structure: 12. A cleaning formulation according to claim 11, comprising 50 to 95% by weight of water, 1 to 10% by weight of at least one surfactant and 0.1 to 10% by weight of component b). A cleaning preparation comprising 1 to 80% by weight of water, 1 to 40% by weight of an alkyl ketal ester, and 0.1 to 10% by weight of a surfactant,
The alkyl ketal ester is represented by the formula (II)

Or formula (III)

Or formula (IV)

Or formula (V)

( Wherein R ⁵ is methyl, ethyl, n-propyl or n-butyl )
A cleaning preparation having the structure: 14. A method for cleaning a soil substrate comprising contacting the composition of any of claims 11-13 with a soil substrate and then removing the cleaning agent of the composition along with the soil removed.